MXPA04004233A - Polyester composite fiber package. - Google Patents
Polyester composite fiber package.Info
- Publication number
- MXPA04004233A MXPA04004233A MXPA04004233A MXPA04004233A MXPA04004233A MX PA04004233 A MXPA04004233 A MX PA04004233A MX PA04004233 A MXPA04004233 A MX PA04004233A MX PA04004233 A MXPA04004233 A MX PA04004233A MX PA04004233 A MXPA04004233 A MX PA04004233A
- Authority
- MX
- Mexico
- Prior art keywords
- coil
- conjugate fiber
- polyester
- fiber
- type
- Prior art date
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H55/00—Wound packages of filamentary material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H2701/00—Handled material; Storage means
- B65H2701/30—Handled filamentary material
- B65H2701/31—Textiles threads or artificial strands of filaments
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Multicomponent Fibers (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Filamentary Materials, Packages, And Safety Devices Therefor (AREA)
Abstract
A composite fiber of polytrimethylene terephthalate is composed of a single yarn in which two kinds of polyester components are bonded into a side-by-side type or an eccentric sheath-core type. At least one of the components constituting the single yarn contains 90mol% or more of repeating unit of trimethylene terephthalate. A lay of the composite fiber is wound in a package by the amount of 2 kg or more. The composite fiber is characterized in that (1) the difference between the winding diameter of the lay at the ear part of the package and that at the central part of the package is 10 mm or less, (2) the winding width of the package is 60 to 250 mm and the winding diameter of the package is 100 to 400 mm, and (3) the difference between the dry heat shrinkage stress of the composite fiber wound at the ear part of the package and that at the central part is 0.05 cN/dtex or less.
Description
FIBER COIL COMPOSED OF POLYESTER TECHNICAL FIELD
The present invention relates to a polyester-type conjugate fiber coil that is obtained by a single-stage melt spinning method, a method for producing the same and a false twist texturing method therefor.
ANTECEDENTS OF THE TECHNIQUE
The polyethylene terephthalate fibers (hereinafter referred to as PET) have been mass produced throughout the world to establish a large industry, because it is more suitable for use in clothing. The polytrimethylene terephthalate fibers (hereinafter referred to as PTT) are known from prior art documents such as J. Polymer Science: Polymer Physics Edition: Vol. 14, p 263 to 274 (1976), Japanese Unexamined Patent Publication (Kokai) No. 52-5320 or O-99/27168. There is a description in the documents in the prior art that a fabric using PTT fibers having the proper characteristics of elongation at break, thermal stress and / or shrinkage in boiling water, have a low modulus to show a smooth feel to the Touch and is suitable for the preparation of clothing such as underwear, outerwear, sportswear, hosiery, underwear or suits. On the other hand, conjugated polyester fibers of a side-by-side type or eccentric sheath-core type have been known as fibers capable of providing a fabric with volume without being subjected to a false twist texturing process. As a PTT-type conjugate fiber characterized by a soft touch feel there is a conjugate fiber in which PTT is used as at least one of its components or a conjugate fiber in which PTT having different inherent viscosities are used, used in both components (these are then referred to as conjugated fibers of the polyester type), as described in Japanese Examined Patent Publication (Kokoku) No. 43-19108, Japanese Unexamined Patent Publications (Kokai) Nos. 11-189923, 2000-239927, 2001-55634, EP 1059372, Japanese Unexamined Patent Publication No. 2001-131837, USP 6306499, WO 01/53573 or US 2002-0025433. These prior art documents disclose that the polyester-type conjugate fiber is characterized by a smooth feel and a favorable waving development property, characteristics which are suitable for various elastic fabrics or bulky fabrics. In general, when a polyester-type conjugate fiber is produced by a melt-spinning method, there is a two-stage method in which an undrawn fiber, once wound as a coil, is stretched to be a stretched fiber, and a one-stage method in which spinning and stretching are carried out in a single process. In Japanese Unexamined Patent Publications (Kokai) Nos. 2001-131837, 2001-348734 and 2002-61030, what is called a direct spinning and stretching method is proposed when conjugate fiber of polyester type is produced, in which the spinning and stretching are carried out continuously in a single step. Particularly, in Japanese Unexamined Patent Publication No. 2001-131837, a stretched conjugated fiber of polyester type is described, which has a stretch elongation of 10% or greater even under a load of 3.5 x 10"3 cN / dtex by controlling the thermal shrinkage tension of the same to be 0.25 cN / dtex or greater.This stretched conjugate fiber of polyester type can be twisted into hard and used for a woven fabric having a large structural restraining force , in which the fiber fabric develops a high curling capacity The methods for obtaining a preoriented fiber to be false twisted are described in Chemical Fibers International: Vol. 47, p 72 to 74 (February, 1997) and in the Japanese Unexamined Patent Publications (okai) Nos. 2001-20136 and 2000-256918. In these documents, as a preoriented fiber to be false twisted, a fiber consisting solely of PTT or a conjugated fiber of polyester type is described, which is wound at a speed of 2000 to 6000 m / min without using a roller extruder or with a cold extruder roller. According to the study of the present inventors, the conjugated pre-oriented polyester-type fiber or the stretched conjugated fiber obtained with a high spinning speed has a high degree of orientation but low crystallinity. Such a preoriented conjugated fiber or stretched conjugate fiber has a vitreous transition temperature in a range of about 35 to 45 ° C and is extremely sensitive to temperature and humidity. In a spinning process, there is a phenomenon in which the heat generation of a motor of a winder that runs at high speed is transmitted to a coil by means of a coil arrow to increase the coil temperature. In addition, the coil temperature is increased by the heat generated due to the friction between the coil and the clamping roller. It has also been evident that, if the coil temperature is increased for such causes, the preoriented conjugated fiber or the drawn conjugate fiber shrinks in the coil during winding. The shrinkage of the preoriented conjugated fiber or of the stretched conjugated fiber is hardly presented in portions of the edge of the coil (hereinafter referred to only as portions of the edge) in which the fiber is laminated to have a high winding hardness, but it only happens in the fiber stratified in the remaining portion (hereinafter referred to as the central portion). As a result, the coil has a large edge shape during winding. Once the large bank shape is formed, the bank portion is alone in contact with the pinch roller and the heat of friction is further concentrated in the portion of the bank as the winding weight of the spool increases. The resulting coil wound in this manner has a predetermined diameter of what is termed a high bank shape wherein a diameter (of winding) of the edge portion is larger than that of the central portion. Figure 1 is a schematic illustration of a coil in a non-high shore shape, and Figure 2 is a schematic illustration of a coil in a high shore shape. The high shore shaped coil not only has a difference and diameter but also has a large difference in fiber property as described below, such as a thermal characteristic, wire fineness and number of corrugations between the shore portion and the central portion. In addition, as the winding weight increases, a side end surface of the coil tends to protrude outwardly due to shrinkage of the fiber to form what is termed a dent making it impossible to remove the coil from the winder. (i) Difference in dry heat shrink stress value The conjugate fibers of polyester type in the edge portion and the central portion of the coil are different from each other in the dry shrink tension value that is obtained by the measurement of the shrinkage stress by heat that is described later. That is, the dry heat shrink tension value of the conjugate fiber in the edge portion is greater than that of the conjugate fiber in the middle portion.
It has been evident that the difference in the characteristic of heat shrinkage becomes evident as a difference in the shrinkage or susceptibility to waving of the fabric during the dyeing process which causes a drawback in terms of appearance quality such as a yarn. tight or wrinkled (ii) Variation in yarn fineness The variation in yarn fineness of a preoriented conjugated fiber or a stretched conjugated fiber is a periodic variation corresponding to a fiber length of one of the coil edge portions with another ( one race or two races). Figures 3 and 4 show diagrams measuring the variation in fineness of preoriented conjugated fiber or stretched conjugate fiber unwound from the coil by a uniformity determiner. Figure 3 is a diagram corresponding to the coil of Figure 1, and Figure 4 is a diagram corresponding to the coil of Figure 2. In the measurement diagrams, periodic variation is observed by signals similar to descending tips. that appear in an equal step on the side of less fineness of thread. The existence of the downward signal means that the fineness of the yarn of the fiber (thickness of the yarn) at this point in the direction of the length of the fiber fluctuates towards the smaller side.
It has been evident that such variation in the fineness of the yarn causes an irregularity in the periodic dyeing in a textured twisted yarn or a fabric, (iii) Apparent curling Polyester type conjugate fiber is characterized by having a susceptibility to curling able to develop curling after heat treatment. However, it can occur in which the ripple has already been developed while the fiber is maintained while being wound on the reel. This is the apparent curly. Since the apparent crimp may cause an increase in unwinding tension when the conjugated polyester fiber is unwound from a coil at high speed, it is preferably lowered. As described above, it has been evident that the winding of conjugated fiber of polyester type in the edge portion of the coil is liable to develop apparent rippling as compared to the coiled fiber in the central portion. For example, the case may be presented in which there is an apparent winding in the bank portion even if there is no apparent winding in the central portion. When the polyester type conjugate fiber is unwound from such a coil at high speed, it has been evident that the unwinding tension fluctuates due to the apparent ripple to generate the yarn break during a false twist texturing process or a weaving process. gone / knit. (iv) High speed unrolling property A flat wavy fabric represented by taffeta or twill or a warp knitted fabric such as a knitted fabric is adopted for garments such as garment or underwear lining. Since raw fiber not processed by false twist texturing or the like is often used for these fabrics, the distribution of the fibers in the fabric is regular. In this way, there is a problem that the drawback exists in the fiber which is apparent directly as a failure in the fabric such as a wavy warp, an undulating weft or an irregular dyeing. Recently, cost competition has become severe in knitting or knitting procedures and processing speed has increased correspondingly. For example, a warp speed in the preparation of warp yarns for woven fabric is increased from a conventional range of 100 to 200 m / min to a current range of 500 to 1000 m / min. In addition, a frame pick-up speed on a loom is as fast as a range of 800 'to 1500 m / min in an industrial process.
If the unwinding tension fluctuation corresponding to the length of the yarn from one end surface to the other end surface of the spool is large during the unwinding of the conjugate fiber of polyester type from the spool at high speed, thread breakage increases. In addition, if the difference between the maximum value and the minimum value of the voltage fluctuation (hereinafter referred to as the difference in unwinding tension) is large, a periodic quality fault occurs in the fabric, such as a tight thread or other failures. Fig. 7 is a diagram showing a fluctuation of the unwinding tension when unrolling a high speed polyester type conjugate fiber from the coil having a favorable winding shape shown in Fig. 1. Fig. 8 is a diagram showing a fluctuation of the unwinding tension when a high speed polyester type conjugate fiber is unwound from the reel having a deflectable winding shape, which is shown in Figure 2. In Figures 7 and 8, a horizontal axis represents the length of yarn of the conjugate fiber of polyester type and the vertical axis represents the tension of unwinding.
Accordingly, in any case where the polyester-type conjugate fiber coil has the drawbacks mentioned above therein, it is used for knitting or knitting as it is without being stretched or when it is used for knitting or knitting after being stretched and subjected to false twisting, the resulting dyed fabric is generally not favorable in terms of uniformity of dyeing and exhibits a periodic irregularity of dyeing or luster. Therefore, it has been evident that the economic value of the fabric which is a final product deteriorates significantly. Such a drawback can not be solved even if the high edge shape of the coil is eliminated to some extent. Any of the coils described in the Japanese Unexamined Patent Publications (okai) Nos. 2001-131837 and 2001-348734 having the periodic drawbacks mentioned above therein due to the heat shrinkage of the conjugated fiber which is large and the High shore shape is significant during the winding process. Accordingly, there has not been a conjugate fiber of the polyester type, obtained by the single-step melt spinning method in the prior art which is capable of producing a fabric that does not exhibit the irregularities of periodic dyeing, a good uniformity of dyeing and excellent appearance, as well as a coil of conjugated fiber of polyester type excellent in its capacity of unwinding at high speed.
DESCRIPTION OF THE INVENTION
An object of the present invention is to provide a polyester-type conjugate fiber coil obtained by a single-stage melt spinning method and suitable for use in garments, the conjugate fiber of the polyester type obtained hereby invention is uniformly unwound from the coil at high speed and is provided to a knitting / idling process as is, without being stretched, or provided to the knitting / weaving process after being subjected to false or stretched twist and Textured The resulting fabric is free from the lack of uniformity of periodic dyeing and is excellent in terms of dyeing uniformity as well as susceptibility properties to stretch and shape recovery after drawing. Another object of the present invention is to provide a method for false twisting of a pre-oriented conjugated fiber of polyester type. The problem to be solved by the present invention is to eliminate the drawbacks of the prior art in a conjugate fiber coil of the polyester type obtained by the melt spinning method in a single step such as the voltage fluctuation during high unwinding. speed, the characteristic of shrinkage by heat, the characteristic of variation of fineness of the thread and the characteristic of ripple that results from the shape of high edge of the coil as well as the lack of uniformity of periodic dyeing in the direction of the length of the thread . The present inventors have diligently studied how to solve the above problems and found that they can be solved by specifying the spinning conditions and the winding conditions of the polyester type conjugate fiber when it is spun and rolled by stretching or not. That is, the present inventors have found that it is possible to eliminate various drawbacks generated in the edge portion of the conjugate fiber coil of polyester type during winding thereof by specifying extrusion conditions and a spinning tension during the process of spinning, a temperature and a winding speed of the coil during the winding thereof in the production of the conjugate fiber. The polyester-type conjugate fiber coil obtained by the above method has the specific range of the heat shrink characteristic and the yarn fineness characteristic of both the shore portion and the central portion., so it is excellent in terms of high speed unwinding properties. The resultant polyester type conjugate fiber can be provided to knit / woven procedures as is without being stretched after being stretched and textured. The fabric obtained is free from the irregularity of periodic dyeing and is excellent in terms of dyeing uniformity as well as its stretch ability and shape recovery property after drawing. The present invention is as follows: 1. A polyester-type conjugate fiber coil either side-by-side or sheath-type / eccentric-core in which two kinds of polyester components adhere to form a filament single, - wherein at least one of the components consists of the single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more, coil in which 2 kg or more of the conjugate fiber and satisfies the following conditions (1) to (3): (1) the difference in diameter between the edge portion and a central portion of the coil is 10 mm or less, (2) the winding width of the coil is in a range of 60 to 250 mm and a bobbin diameter is in a range of 100 to 400 mm, and (3) the difference in the shrinkage stress value by dry heat between the conjugate fibers stratified in the portion of shore and the portion n core coil is 0.05 cN / dtex or less. 2. A polyester type conjugate fiber coil as defined by the preceding subsection 1, wherein the difference in the dry heat shrink stress value between the conjugate fibers stratified in the edge portion and the central portion of the coil is 0.01 cN / dtex or less. 3. A polyester-type conjugate fiber coil as defined in preceding paragraphs 1 or 2, wherein the conjugate fiber stratified in the coil is a pre-oriented conjugate fiber having an elongation toward rupture in a range of 60 to 120 %. 4. A polyester-type conjugate fiber coil as defined in preceding paragraphs 1 and 2, wherein the conjugate fiber stratified in the coil is a stretched conjugate fiber having an elongation to rupture in a range of 25 to 80 %. 5. A polyester-type conjugate fiber coil as described in any of the foregoing paragraphs 1 to 4, wherein the U% value of yarn fineness variation of the unwound conjugate fiber of the coil is 1.5% or less , and a coefficient of variation of a yarn fineness variation period is 0.4 or less. 6. A polyester-type conjugate fiber coil as defined in any of the foregoing paragraphs 1 to 5, wherein the ratio between the difference AF (cN / dtex) in the unwinding tension during unwinding of the conjugate fiber from the coil an uncoiling speed u (m / min) satisfies the following formula (1): AF <; 8.0 x 10 ~ 6 u (1) 7. A polyester-type conjugate fiber coil as defined in any of the preceding paragraphs 1 to 6, wherein a percentage of the coil dent is 12% or less. 8. A polyester-type conjugate fiber coil as defined in any of items 1 to 7, wherein the stretch elongation Ve of the stratified conjugate fiber in the edge portion of the coil is 20% or less before be treated with boiling water. 9. A coil of polyester-type conjugate fiber as defined in any of the foregoing paragraphs 1 to 8, wherein the hardness of the edge portion of the coil is in a range of 50 to 90 and the difference in hardness between the opposite shore portions is 10 or less. 10. A polyester-type conjugate fiber coil as defined in any of the foregoing paragraphs 1 to 9, wherein the coil density is in a range of 0.80 to 0.92 g / cm3. 11. A polyester-type conjugate fiber coil as defined in any of preceding paragraphs 1 to 10, wherein either of the two kinds of polyester components is polytrimethylene terephthalate containing 90 mole percent or more of the units repeated of trimethylene terephthalate. 12. A pre-oriented conjugate fiber of the polyester type of the side-to-side type or the eccentric sheath-core type in which two kinds of polyester components adhere to each other to form a single filament, wherein at least one of the components consisting of a single filament is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mole percent or more, and wherein the preoriented conjugated fiber is coiled to form a coil that satisfies the following conditions (1) a (4): (1) A stretched elongation before being treated with boiling water, which is less than 20%, (2) an elongation at break that is in a range of 60 to 120%, (3) a value of dry heat shrinkage tension that is in a range of 0.01 to 0.15 cN / dtex, and (4) a U value of variation of fineness of yarn that is 1.5% or less and a coefficient of variation of the period of yarn fineness variation that is 0.4 or less. 13. A stretched conjugate fiber of the polyester type of the side-to-side type or the eccentric sheath-core type in which two kinds of polyester components adhere to each other to form a single filament, wherein at least one of the components consists of a single filament is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more, and wherein the drawn conjugate fiber is wound to form a coil that satisfies the following conditions (5) to ( 8): (5) a stretch elongation CE2 measured after the conjugate fiber has been treated with boiling water under a load of 2 x 10"3 cN / dtex which is in a range of 5 to 100%, (6) ) an elongation at break that is in a range of 25 to 80%, (7) a dry heat shrink stress value that is in a range of 0.02 to 0.24 cN / dtex, and (8) a U% value of yarn fineness variation that is 1.5% or less and a coefficient e of variation of the yarn fineness variation period that is 0.4 or less. 14. The conjugate fiber of polyester type as defined in the preceding paragraphs 12 or 13, wherein the fiber-fiber dynamic friction coefficient of the conjugate fiber is in a range of 0.20 to 0.35 and the difference between the maximum and Minimum of the coefficient of dynamic friction in the direction of yarn length is 0.05 or less. 15. The conjugate fiber of the polyester type as defined in the preceding paragraphs 12 or 14, wherein the difference in the direction of the yarn length between the maximum and minimum values of a tension value at 10% elongation in the measurement of tensions and elongations is 0.30 cN / dtex or less. 16. The conjugate fiber of polyester type as defined in the preceding paragraphs 12 or 15, wherein the modified cross-sectional degree of the conjugate fiber is in a range of 1 to 5. 17. Faux torsion-textured yarn of conjugated fiber of polyester type obtained by false twist texturing of the conjugated fiber of polyester type defined by any of the foregoing paragraphs 1 to 16, which satisfies the following conditions (a) and (b): (a) a tensile strength that is in a range of 2 to 4 cN / dtex, and (b) a Stretch elongation CE2 measured after being treated with boiling water under a load of 2 x 1CT3 cN / dtex which is in a range of 50 to 250%. 18. A method for producing a polyester type conjugate fiber coil of the side-to-side type or the eccentric sheath / core type in which two kinds of polyester components adhere to form a single filament, thus minus one of the components consists of a single filament that is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or greater; and the conjugate fiber is spun by the melt spinning method and is wound on a coil while cooling and solidifying by cooling air, in which the spinning process is carried out by maintaining a spinning tension at 0.3 cN / dtex or less, a coil temperature of 30 ° C or less and a winding speed in a range of 1500 to 4000 m / min. 19. A method for producing a pre-oriented conjugate fiber coil of the polyester type of the side-to-side type or the eccentric sheath / core type in which two kinds of polyester components adhere to form a single filament, at least one of the components consists of a single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or greater; and the conjugate fiber is spun by the melt spinning method and is wound onto a coil without stretching the conjugate fiber after it is cooled and solidified by cooling air, wherein the winding is carried out under the condition satisfying the following conditions (a) to (e) ·. (a) a spinneret is used to secure the spinning condition after joining together the two kinds of polyester components having a dimensional ratio L / D of 2 or 'greater where L is the hole length and D is the hole diameter and an orifice inclined at an angle of 10 to 40 ° relative to the vertical direction, (b) the spinning tension is in a range of
0. 10 to 0.30 cN / dtex, (c) the heat treatment temperature is in a range of 70 to 120 ° C and the heat treatment tension is in a range of 0.02 to 0.10 cN / dtex, (d) the temperature of coil is 30 ° C or less when the conjugate fiber is wound on the coiler, and (e) the winding speed is in a range of 1,500 to 4,000 m / min. 20. A method for producing a polyester type conjugate fiber coil of the side-to-side type or sheath / eccentric core type in which two kinds of polyester components adhere to form a single filament; at least one of the components consists of a single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or greater; and the conjugate fiber is spun by the melt spinning method and is wound on a coil as drawn conjugate fiber obtained by drawing directly from the conjugate fiber without having been wound once in the coil after being cooled and solidified by cooling air , where the winding is carried out under the condition that they satisfy the following conditions (a) and (f) to (h): (a) a spinneret is used to ensure the condition of spinning after they are joined by joining two kinds of polyester components having a dimensional ratio L / D of 2 or greater where L is the hole length and D is the hole diameter and a hole inclined at an angle of 10 to 40 ° relative to the direction vertical, (f) the drawing tension is in a range of 0.05 to 0.40 cN / dtex, (g) a speed VR of the heated second drawing roll is in a range of 2,000 to 4,000 m / min, (h) a VW ratio / VR of a speed of winding Vw (m / min) at the speed VR (m / min) of the second heated drawing roller satisfies the following formula (2): 0.85 = VW / VR = 1 (2) e (i) the winding temperature, when the conjugate fiber is wound on the winder, it is 30 ° C or less. 21. A method for producing a polyester-type conjugate fiber coil as defined by the preceding subsection 20, wherein heat treatment under tension is carried out between the heated second drawing roll and a heated third drawing roll. 22. A method for producing a polyester-type conjugate fiber coil as defined by any of the preceding subparagraphs 18 to 21, wherein the transverse angle of the coil is changed from the start to the end of the coil formation. in a range of 3 to 10 ° in correspondence with the winding diameter of the coil. 23. A method for fake twist texturing preoriented conjugated fiber of polyester type of the side-to-side type or sheath / eccentric core type in which two kinds of polyester components adhere to form a single filament; at least one of the components consists of a single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more; and the conjugate fiber is spun by a melt spinning method and wound on the coil as a preoriented conjugate fiber obtained without being stretched after it is cooled and solidified by cooling air, where the spinning tension is controlled at 0.30 cN / dtex or less the coil temperature during the winding is maintained at 30 ° C or less, and the texturing by false and stretched twist or the false twist texturing is done by keeping the temperature of the conjugate fiber preorientated by 30 ° C not only during the winding procedure but also during the storage period as well as in the false twist texturing procedure thereof. In this regard, the conjugate fiber referred to in the present invention includes a preoriented conjugated fiber which is wound without being stretched after the melt spinning process and a stretched conjugate fiber which is wound after being spun and stretched continuously (by what is called the direct spinning-stretching method). The present invention will be described in greater detail in the following.
The polyester type conjugate fiber coil according to the present invention is produced from a group of single filaments in which two kinds of polyester components adhere to each other, in a single filament, side-by-side or in a sheath / eccentric core wherein at least one component constituting the single filament consists solely of PTT. The two kinds of polyester component can be adhered together in a side-by-side manner along the longitudinal direction of the yarn or they can be of the eccentric sheath-core type in which one of the polyester components is embedded partially or completely in the other polyester component so that both components are distributed eccentrically in the cross section of the fiber. The side-to-side type is preferable. If PTT is used as a component, the development of ripple in the conjugate fiber or the yarn textured by false twist becomes favorable, while there is no limitation in the other components, preferably it is selected from polyethylene terephthalate (PET), terephthalate polytrimethylene (PTT) and polybutylene terephthalate (PBT) in view of the adhesiveness with PTT. It is more preferable that both kinds of polyester components are PTT. The difference in intrinsic viscosity between the two kinds of polyester components is preferably in a range of 0.05 to 0.08 dl / g. When the difference in intrinsic viscosity is within this range, the development of crimping becomes sufficient and the yarn that bends directly below the spinneret is smaller to minimize thread breakage. When the two kinds of polyester component are PTT, respectively, the difference in intrinsic viscosity is preferably in a range of 0.1 to 0.4 dl / g, more preferably 0.1 to 0.25 dl / g. An average intrinsic viscosity of the conjugate fiber consisting of the PTT is preferably in a range of 0.7 to 1.2 dl / g, more preferably 0.8 to 1.1 dl / g. If the average intrinsic viscosity is in the aforementioned range, the strength of the conjugate fiber becomes approximately 2 cN / dtex or more to be applicable to the field of sportswear requiring strength. In the present invention, a proportion of the two kinds of polyester components in the cross section of the single filament preferably is in a range of 40/60 to 70/30, more preferably 45/55 to 65/35, in where the denominator is a component having a lower intrinsic viscosity and the numerator is a component having a higher intrinsic viscosity. If the ratio is within the above range, ripple operation is facilitated and a conjugate fiber strength as high as 2.5 cN / dtex or greater is generated, which is suitable for use in sportswear. The PTT polymer constituting at least one of the components of the polyester-type conjugated fiber according to the present invention contains repeating units of trimethylene terephthalate of 90 mole percent or more, and other repeating units of these of 10 moles. % or less. That is, at least one of the components of the polyester type conjugate fiber according to the present invention is an ompolimer of PTT or a PTT copolymer containing 10 moles or less of other ester repeat units, such as a copolymer component. . Examples of the copolymer component are the following: As an acid component, there is an aromatic dicarboxylic acid represented by isophthalic acid or sodium 5-sulfoisophthalic acid and the aliphatic dicarboxylic acid represented by adipic acid or itaconic acid. As a glycol component, there is ethylene glycol, butylene glycol and polyethylene glycol. In addition, hydroxycarboxylic acid such as hydroxybenzoic acid is an example thereof. A plurality thereof may be copolymerized. Preferably a trifunctional crosslinking component such as trimellitic acid is avoided, pentaerythritol or pyromellitic acid, in some cases, as a copolymerized component because it alters the spin stability or decreases the elongation at break of the textured yarn by false twisting, resulting in an increase in yarn breakage during the process of textured by false twist. Known methods for the production of the PTT polymer of the present invention can be used. For example, there is a one-step method where a degree of polymerization is obtained corresponding to an intrinsic viscosity predetermined only by melt polymerization and a two-stage method where melt polymerization is used until a certain degree of polymerization is obtained. intrinsic viscosity and then the solid state polymerization is used to increase the degree of polymerization to a value corresponding to a predetermined intrinsic viscosity. The latter two-stage method combined with the solid state polymerization is preferable because it can reduce the cyclic dimer content in the polymer. When the predetermined intrinsic viscosity is obtained by the single-stage method, the cyclic dimer in the polymer is preferably reduced before being supplied to the spinning process by the extraction treatment or others.
The cyclic dimer content of trimethylene terephthalate in the PTT polymer used for the present invention is preferably 2.5% by weight or less, more preferably 1.1% by weight or less, moreover, preferably 1.0% by weight or less. In addition, the additives can be mixed or copolymerized with the PTT polymer within a range that does not alter the effect of the present invention, such as titanium oxide as a delustrant, heat stabilizer, antioxidant, antistatic agent, substance that absorbs radiation ultraviolet, antimicrobial agent or various pigments. The polyester-type conjugate fiber coil according to the present invention has a winding weight of 2 kg or more. If the winding weight is less than 2 kg, it is necessary to frequently interchange the coils during the false twist texturing process or the knitting / weaving process, which is not economically advantageous due to the increments of work and the increase in operating costs. The winding weight is preferably about 3 kg or more, more preferably about 4 kg or more. The upper limit of the winding weight will be approximately 20 kg in view of the manual handling by the operator, although it is not particularly limited.
The polyester-type conjugate fiber coil according to the present invention has a difference in winding diameter in a range of 0 to 100 mm between the edge portion and the central portion of the coil. The difference in the winding diameter between the edge portion and the central portion of the winding is an index that represents a degree of what is termed a high bank shape. If the winding diameter is less than about 100 mm, the difference in winding diameter is not significant. However, if the winding diameter exceeds approximately 200 mm, the difference in winding diameter increases. When the difference in the winding diameter exceeds 10 mm, the period of variation of yarn fineness becomes significant in a measurement of yarn fineness variation, explained below. If the period of yarn fineness variation becomes significant, an irregularity of periodic dyeing occurs in the resulting fabric. To avoid irregularity of periodic dyeing in the fabric, the difference in winding diameter is more preferably 5 mm or less, much more preferably 3 mm or less. The conjugate fiber coil of polyester type according to the present invention has a winding diameter of 100 mm or more, preferably in a range of 150 to 400 mm. If the winding diameter is 100 mm or greater, the winding height becomes 2 kg or more to provide a coil suitable for industrial use. If the winding diameter is less than 100 mm the winding weight becomes insufficient to increase the costs of the polyester type conjugate fiber when the price of a paper tube of a spool for the spool is added thereto. In addition, there is an industrial disadvantage in that the wrapping material, the cost of packaging and the transportation cost for the packaging become comparatively high. · A winding width of the conjugate fiber coil of polyester type is in a range of 60 to 250 mm, preferably 80 to 200 mm. If the winding width is less than 60 mm, the winding diameter must be too large to obtain the winding weight of 2 kg or more, which results in difficulty of industrial handling thereof. When the winding width is small, the ratio of the edge portion to the winding width becomes large which causes a coil with a high edge shape. Conversely, if the winding width exceeds 250 mm, the unwinding tension fluctuation becomes large during unwinding of the conjugate fiber from the coil although the high edge shape is corrected to be as small as possible., resulting in irregularity of periodic dyeing in the resulting fabric and yarn breakage during the unwinding of the fiber at high speed. The dry heat shrinkage stress of the polyester type conjugate fiber is a force of shrinkage of the fiber due to heat and measured by a method described below. The stratified polyester type conjugate fiber in the edge portion of the coil is capable of exhibiting a dry heat shrink tension value greater than that of the stratified fiber in the central portion of the coil. In the present invention, it is important that the difference, in the dry heat shrink tension value between the stratified fibers in the edge portion and in the central portion is 0.05 cN / dtex or less. If the difference in shrinkage stress value by dry heat exceeds 0.05 cN / dtex, the resulting fabric presents abnormalities in the stratified fiber in the edge portion, such as a periodic tight thread or an irregularity in the dyeing to deteriorate the appearance quality of the resulting fabric. This difference in the shrinkage stress value by dry heat is preferably as small as possible and preferably is 0.01 cN / dtex or less, more preferably 0.005 cN / dtex or less. If there is no difference, it is in the most favorable state. In preferred aspect of the conjugated fiber of polyester type according to the present invention will be described below. (Variation of the fineness of the yarn) Preferably, in the present invention, the value U% of yarn fineness variation of the unwound conjugate fiber of the bobbin is 1.5% or less and the coefficient of variation of the fineness variation period. of yarn is 0.4 or less. If the value U% of fineness variation of yarn is 1.5% or less, an excellent fabric is obtained in dyeing uniformity. A U% value of yarn fineness variation is preferably 1.2% or less, more preferably 1.0% or less. If the coefficient of variation is 0.4 or less, an excellent fabric can be obtained in terms of appearance quality. The coefficient of variation is preferably as small as possible. In particular, it is favorable that it be 0.2% or less. When the coefficient of variation of the yarn fineness variation period exceeds 0.4 even if the yarn fineness variation value U% is 1.5% or less, abnormalities in dyeing in the resulting fabric are caused by the portion of the conjugate fiber coil edge of polyester type, so that a fabric having a favorable appearance quality can not be obtained. For example, a woven fabric having a dense structure of warp and weft yarns is liable to exhibit the aforementioned dyeing abnormality. Particularly, such an abnormality often occurs when a preoriented fiber is used as such for a knitting / weaving process, without undergoing a false and stretched twist texturing process. As described later, the coefficient of variation. it is determined by the periodic analysis of the fineness variation of yarn accompanied by the measurement of yarn fineness variation. - Figure 5 is a diagram of the periodic analysis of the variation of fineness of yarn in correspondence with Figure 3 and Figure 6 is a diagram of the periodic analysis of the variation of fineness of yarn in correspondence with Figure 4. In these diagrams of analysis, the horizontal axis represents a periodic length and the vertical axis represents a frequency (coefficient of variation). In the periodic analysis of the yarn fineness variation, the periodic length corresponds to a length of yarn measured from one edge to the other of the conjugate fiber coil of polyester type. Although the length of the yarn can vary according to the transverse width when the coil is formed, is generally found in a range of 0.5 to 10 m. The signals caused by the variation of fineness of yarn in the edge portion appear as specific peaks of the coefficient of variation at a constant periodic length, as shown in Figure 6. (Fluctuation of the unwinding tension) The conjugate fiber coil of polyester type according to the present invention preferably satisfies the following formula which defines the ratio between the difference AF (cN / dtex) in the tension of unwinding and the speed u of unwinding (m / min), when unwinding the conjugate fiber wound on the coil. AF = 8.0 x 10"su (1) The formula (1) shows the influence of the unwinding speed on the unwinding tension when unwinding conjugate fiber coiled in the coil If the difference in unwinding tension is within the range defined by the formula (1) there is no yarn break in the knitting / weaving process and the false twist texturing procedure for the unwinding tension fluctuation or a fabric failure such as a tight yarn or abnormality arrested.
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For the purpose of assisting in the compression of formula (1), an area in which the difference between unwinding tension is favorable is shown with diagonal lines in Figure 9. For example, if the speed of the unwound fiber at From the conjugate fiber coil of polyester type is 1000 m / min, the difference in unwind tension AF (cN / dtex) is preferably 0.008 cN / dtex or less. (Stretch elongation before being treated with boiling water) Stretch elongation Before treated with boiling water, the stratified conjugate yarn in the edge portion of the coil is preferably 20% or less, more preferably 10% or less. The conjugate fiber stratified in the edge portion of the coil is capable of having a high stretch elongation before being treated with boiling water, compared to the conjugate fiber stratified in the central portion. However, if the stretch elongation before being treated with boiling water is 20% or less, the unwinding strength is small when the conjugate fiber is unwound from the coil? therefore there is no tension fluctuation or yarn break even at a high unwinding speed. (Winding hardness) - -
The winding hardness of the edge portion of the coil preferably is in a range of 50 to 90. In addition, the difference in winding hardness between the opposite edge portions is preferably 10 or less. When the winding hardness of the edge portion is within the range mentioned above, the coil does not collapse during transport or handling, and since the unwind resistance is small when the conjugate fiber is unwound from the edge portion, it does not collapse. there is tension fluctuation or yarn break even at a high unwinding speed. A favorable range of winding hardness of the edge portion is from 60 to 85. When the difference in winding hardness between the opposite shore portions; that is, between one edge portion and the other edge portion is 10 or less, there is no tight thread or abnormality of dyeing in the resulting fabric because the difference in unwinding tension becomes small between both edge portions. . (Winding density) The winding density of the coil is preferably in a range of 0.80 to 0.92 g / cm3, more preferably 0.82 to 0.90 g / cm3. When the winding density is within the mentioned range - -
before, there is no collapse of the coil during transport or handling thereof and, since the unwinding resistance becomes small, there is no voltage fluctuation or yarn break even at high unwinding speed. (Dents) The percentage of dents of the polyester-type conjugate fiber coil according to the present invention is preferably 12% or less, more preferably 10% less, and even more preferably 8% or less. Of course, the most preferable is 0%. When the percentage of dent is 12% or less, the tightness of the winding of the coil due to the shrinkage of the conjugate fiber is less, so that it is possible to easily separate the coil from a use of the coiler, in addition, as that the end of the bobbin does not come into contact with the wrapping material when the bobbin is packaged, the conjugate fiber unwinds uniformly from the bobbin during the unwinding process. The particular conditions for the preoriented conjugate fiber coil of polyester type according to the present invention will be described in the following. The pre-oriented conjugated fiber of the polyester type is wound in a coil and simultaneously satisfies the following conditions (1) to (4): - -
(1) The stretch elongation Ve before being treated with boiling water is less than 20%, (2) the elongation at break is in a range of 60 to 120%, (3) the value of shrinkage stress per dry heat is in a range of 0.01 to 0.15 cN / dtex), and (4) the value U% of yarn fineness variation is 1.5% or less and the coefficient of variation of the yarn fineness variation period is 0.4 or less. In the present invention, stretching elongation
It sees before being treated with boiling water the preoriented conjugated fiber of polyester type is less than 20%, preferably 15% or less, and more preferably 10% or less. If the stretched elongation before being treated with boiling water is less than 20%, a contact resistance of the fiber with guides or others becomes small during the high-speed false twist texturing process or the texturing procedure of false twisting and stretching at high speed and therefore there is no breakage of thread or fluff. In the present invention, the elongation at break of the pre-oriented conjugated fiber of polyester type is in a range of 60 to 120%, preferably 70 to 100%. The pre-oriented conjugated fiber that has the elongation to rupture within the range - -
mentioned above can be obtained at a winding speed of about 4000 m / min or less to produce a coil having a smaller shore height, which does not collapse even if it is stored for a prolonged period. In the present invention, the dry heat shrink strain value of the pre-oriented conjugated fiber of polyester type is in a range of 0.01 to 0.15 cN / detex, preferably 0.03 to 0.10 cN / dtex. If the dry heat shrink tension value is within the range mentioned above, a coil having a smaller shore height which is free of yarn breakage during winding thereof is produced. Although the dry heat shrink tension value is preferably as small as possible, it is difficult to produce a fiber having a shrinkage stress value by dry heat of less than 0.01. In the present invention, the U% value of yarn fineness variation of the pre-oriented conjugated fiber of polyester type is 1.5% or less and the coefficient of variation of the yarn fineness variation period is 0.4 or less. If the value U% of fineness variation of yarn is 1.5% or less, the resulting fabric is excellent in terms of dyeing uniformity. The value U% fineness variation of - -
yarn preferably is 1.2% or less, more preferably 1.0% or less. If the coefficient of variation is 0.4 or less, the resulting fabric has excellent appearance quality. The coefficient of variation is preferably as small as possible. A value of 0.3 or less is particularly favorable. When the coefficient of variation of the yarn fineness variation period exceeds 0.4, an abnormality of dyeing in the resulting fabric caused by the edge portion of the polyester type conjugate fiber coil may occur even if the coefficient of variation U% is 1.5% or less, which deteriorates the appearance quality of the fabric. For example, in a woven fabric in which the warp threads and the weft threads are densely woven together, such a dyeing abnormality is liable to occur. Particularly, this phenomenon is important when the preoriented conjugated fiber is supplied to a knitting / weaving process as it is without undergoing the false and stretched twist texturing process. The calorific value of crystallization as measured by differential scanning calorimetry (DSC) of the pre-oriented conjugated fiber of polyester type is preferably 10 J / g or less, more preferably 5 J / g or less, still more preferably 2 J / or less, if the value - -
Crystallization calorific is 10 J / g or less, the advance of auto-crystallization of the conjugated fiber preorientated at an elevated temperature is limited. Preferably the calorific value of crystallization is as small as possible. The calorific value of crystallization by differential scanning calorimetry (DSC) is a value obtained by the measurement described later. The calorific value of crystallization is a calorie generated when the preoriented conjugated fiber is crystallized, which is a measure of the degree of crystallization. The lower the calorific value of crystallization, the greater the crystallization of the conjugate fiber preorientated. The calorific value of crystallization of a pre-oriented conjugated fiber of the polyester type in which the crystallization progresses hardly exceeds about 10 J / g. On the other hand, when the crystallization has advanced sufficiently, the calorific value of crystallization becomes 0 J / g according to this method, and measurement is impossible. One of the advantages of the pre-oriented conjugate fiber in which crystallization has advanced is that when the preoriented conjugated fiber is supplied to a false and stretched twist texturing process and is kept in a warm environment at about 40 ° C.
or greater for a prolonged period, the advancement of the auto-crystallization of the conjugated fiber preorientated is limited. In accordance with this effect, the high edge shape and the deformation of the coil is reduced, thereby minimizing the presentation of dye abnormalities of the textured yarn by false twisting. Another advantage is that the preoriented conjugate fiber can be supplied to a knitting / weaving process without being subjected to a false and stretched twist texturing process resulting in an excellent fabric in appearance quality. In the following, the peculiar conditions for the winding of stretched conjugated fiber of polyester type according to the present invention will be described below. The conjugated and stretched fiber of the polyester type is wound on a coil and simultaneously satisfies the following conditions (5) to (8): (5) the stretch elongation CE2 measured under a load of 2 x 10"3 cN / dtex after to be treated with boiling water is in a range of 5 to 100%. (G) the elongation at break is in a range of 25 to 80%, (7) the value of shrinkage stress by dry heat is in a interval of 0.02 to 0.24 cN / dtex, and (8) the value U% of fineness variation of yarn is 1.5% or less and the coefficient of variation of the yarn fineness variation period is 0.4 or less. present invention, the stretch elongation CE2 measured under a load of 2 x 10"3 cN / dtex after being treated with boiling water is in a range of 5 to 100%, preferably 10 to 100%, and more preferable from 20 to 100%. If the stretch elongation CE2 is within the range mentioned above, the resulting fabric is excellent in its susceptibility to drawing. In this regard, it is difficult to obtain 100% or more of this value, according to current technology. The larger the stretch elongation CE2, the greater the susceptibility to drawing even in a structure fabric having a high restraining force such as a woven fabric. In the present invention, the elongation at break of a stretched conjugated fiber of polyester type is in a range of 25 to 80%, preferably 30 to 60%. If the elongation at break is 25% or greater, it is possible to produce the fiber in a stable manner without thread breakage during stretching and a coil of the same has a low edge height 'so no abnormalities occur. dyed in the resulting fabric. If the elongation at break is 80% or less, the resistance to - -
The pull of the conjugate fiber is approximately 2 cN / dtex or greater and is usable for a sportswear application that requires high traction. In addition, there are no abnormalities of dyeing of the thick and thin type. In the present invention, the dry heat shrink tension value of the stretched conjugated fiber of polyester type is in a range of 0.02 to 0.24 cN / dtex, preferably 0.05 to 0.15 cN / dtex. If the dry heat shrink tension value is within the range mentioned above, it is possible to produce a coil having a low shore height. The shrinkage stress value for dry heat is preferably as small as possible. However, the production of the fiber that has this value of less than 0.02 is difficult because there is often thread breakage during the winding. In the present invention, the U% value of yarn fineness variation of the drawn conjugate fiber is 1.5 or less and the variation coefficient of the yarn fineness variation period is preferably 0.4 or less. If the value U% of yarn fineness variation is 1.5% or less, an excellent fabric in dyeing uniformity can be obtained. The U% value of yarn fineness variation preferably is 1.2% or less, more preferably 1.0% or less.
If the coefficient of variation is 0.4 or less, an excellent fabric can be obtained in appearance quality. The coefficient of variation is preferably as small as possible and 0.3 or less is particularly favorable. When the coefficient of variation of the yarn fineness variation period exceeds 0.4, can be presented to the case in which it occurs in dye abnormalities in the resulting fabric due to the edge portion of the conjugate fiber coil stretched to degrade the fabric even if the U% value of yarn fineness variation is 1.5 % or less. For example, this tendency is significant in a woven fabric in which the warp yarn and the weft yarn are densely interwoven, particularly when the stretched conjugate fiber is supplied to a knitting / weaving process as it is without being subjected to a process of false twist texturing. The favorable conditions common to the polyester type pre-oriented conjugate fiber and the polyester type stretched conjugate fiber will be described below: Preferably, the fiber / fiber dynamic friction coefficient is in a range of 0.20 to 0.35 and the difference in the same, I entered the maximum and minimum values in the direction of thread length is 0.05 or less.
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If the fiber-fiber dynamic friction coefficient is within the range mentioned above, it is possible to produce a coil of 2 kg or more since the fiber does not slip off of the coil. Furthermore, since the unwinding tension becomes small when the conjugate fiber is unwound from the spool, there is no thread breakage or abnormalities in the dyeing. If the difference in the coefficient of friction between the maximum and minimum values in the direction of the yarn length is 0.5 or less, it is possible to further reduce the fluctuation of the unwinding tension. The difference in the stress value at 10% elongation in the measurement of stresses and elongations between the maximum and minimum values is preferably 0.30 cN / dtex or less in the direction of the yarn length. The present inventors have found that a tension value at 10% elongation of the measurements of stresses and elongations has a good correspondence with the uniformity of dyeing in the yarn length direction and if the difference between the maximum and minimum values is of 0.30 cN / dtex or less in the yarn length direction, excellent fabric can be obtained in dye uniformity. The difference in the tension value at 10% elongation between the maximum and minimum values is preferably as small as possible and if it is 0.2 cN / dtex or less, an additional excellent fabric can be obtained in dye uniformity. Although there is no limitation with respect to the fineness of the yarn or the fineness of a single filament of the conjugated fiber of polyester type, the yarn fineness preferably is in a range of 20 to 300 dtex and the single filament fineness preferably is in a range from 0.5 to 20 dtex. There is no limitation on the single filament cross section, which may include a modified cross section different from a circle, such as a triangle, an oval, a flat shape, a W shape or an X shape. Particularly, it is possible to show excellent dyeing uniformity as well as a good susceptibility to stretching if the modified cross section degree is in a range of 1 to 5. In the present invention, the polyester type conjugate fiber can be used as a long filament yarn or short fibers that are cut into a length in a range of 20 to 200 trun. In either case, excellent dyeing uniformity as well as good susceptibility to drawing can be obtained. The conjugated fiber of polyester type according to the present invention can be mixed or copolymerized with delustrant titanium oxide, thermal stabilizers, antioxidants, static agents, substances - -
ultraviolet radiation absorbers, antifungal agents or various pigments unless they alter the effect of the present invention. In addition, a finishing agent in a range of 0.2 to 2% by weight is preferably applied to the conjugate fiber of the polyester type for the purpose of imparting a fineness, filament cohesion and antistatic properties to the fiber. In addition, for the purpose of improving the unwinding property and filament cohesion during unwinding or a false twist texturing process, the single filaments can be intertwined with each other at 2 to 50 dots / m. A method for producing a conjugate fiber coil of polyester type according to the present invention will be described below. The polyester type conjugate fiber coil according to the present invention can be produced by a conjugate fiber spinning apparatus including a spinneret and a double arrow extruder described in the following. Figure 10 illustrates a schematic view of an example of a die used for the production of the polyester type conjugate fiber coil according to the present invention. In figure 10, (a) indicates a distributor and (b) indicates a spinning nozzle. The two kinds of polyesters having different intrinsic viscosity values are introduced from P and Q, respectively, and fed to the spinning nozzle (b) from the distributor (a). After both are joined at the spinning nozzle (b), the joined stream is extruded from the spin hole inclined at T degrees relative to the vertical direction. A diameter of the orifice is represented by D and the length thereof is represented by L. In the present invention, the ratio of the length L to the diameter D (L / D) is preferably 2 or greater. If L / D is 2 or more, both components having different intrinsic viscosity values will stably adhere to each other after they have been joined so that no vibration will be generated in the extruded stream. In this way, it is possible to maintain the value U% of yarn fineness variation of the resulting fiber within the range defined by the present invention. The L / D ratio is preferably as large as possible. However, in view of the manufacturing facility of the die, the L / D ratio is more preferably in a range of 2 to 8, and preferably additionally 2.5 to 5. In the present invention, the Spinning has the inclination in a range of 10 to 40 degrees in relation to the vertical direction. The angle of inclination of the spin hole relative to the vertical line is represented by T (degrees) in Figure 10. This inclination of the spin hole relative to the vertical direction is an important condition to prevent bends from occurring in the vertical direction. yarn due to the difference in intrinsic viscosity between the two kinds of polyester components. If there is no inclination in the spin hole, the filament thread, extruded from the orifice, is liable to bend towards the side with higher intrinsic viscosity since the difference in intrinsic viscosity is larger. This is called a bending phenomenon that alters a stable yarn. In addition, the value U% of yarn fineness variation of the resulting conjugated fiber becomes larger which deteriorates the uniformity in the dyeing. In Fig. 10, preferably, the polyester having a higher intrinsic viscosity is supplied on the P side and the one having a lower intrinsic viscosity is supplied on the Q side. Fig. 11 is a schematic illustration of an example of an apparatus of yarn used to carry out the method according to the present invention. Based on this drawing, a preferable production method will be described. In Figure 11, pellets of a polyester component are dried by means of a dryer 1 to present a moisture content of 20 ppm or less and are supplied to an extruder 2 which is maintained at a temperature in a range of 250 to 280. ° C in which the pellets are melted. The pellets of another polyester component are also supplied to an extruder 4 by means of a dryer 3 and are melted in the same manner as indicated above. The fused polyester components are supplied by means of the folds 5 and 6, respectively, to a spinning head 7 which is maintained at a temperature in a range of 250 to 285 ° C, and are weighed separately by means of pumps. gear. Then, the two kinds of components are joined in a row 9 which has a plurality of holes and are mounted in a spin pack or coil 8. After they adhere to each other to form a side-to-side conjugate fiber or eccentric sheath / core type, the components are extruded into a spin chamber as a filament thread of the conjugate fiber 10. The optimum temperature of the The extruder and the spinning head are selected from the aforementioned range according to the classes of intrinsic viscosity values of the polyester. The strand 10 of extruded filament in the spinning chamber is cooled, by cooling air 12, to ambient temperature and solidifies. After a finishing agent is imparted by means of a finishing agent applicator 13, the filament yarn is captured by a first stretching roller 14 rotating at a predetermined speed. The finishing agent is preferably a type of aqueous emulsion, a concentration of which preferably is 10% by weight or greater, more preferably in a range of 10 to 30% by weight. The finishing agent preferably contains fatty acid ester and / or mineral agent in a range of 10 to 80% by weight or polyether having a molecular weight of 1000 to 20,000 in a range of 50 to 98% by weight, which preferably, the fiber is imparted in a range of 0.3 to 1.5% by weight. By applying such a finishing agent, it is possible to control the fiber-fiber dynamic friction coefficient within a range of 0.2 to 0.35 so as to improve the uncoiling property of the conjugate fiber from the coil and prevent it from occurring yarn breakage during the false twist texturing process of the knitting / weaving process. If necessary, an interleaver may be provided between the finishing agent applicator 13 and the first stretching roller 14, between the first drawing roller 14 and a second drawing roller 15 or between the second drawing roller 15 and a winder for imparting to the thread an interlaced. The interleaver can be of a type - -
known in which the fluid pressure is preferably adjusted to a value in a range of 0.01 to 0.6 MPa to impart to the yarn an interlacing in a range of 2 to 50 dots / m. According to the present invention, the spinning tension is 0.30 cN / dtex or less, preferably 0.20 cN / dtex or less, and more preferably 0.15 cN / dtex or less. The spinning tension is preferably as small as possible. However, if this value is 0.3 cN / dtex or less, it is possible to continuously produce the fiber in a stable state because there is no yarn breakage caused by frictional abrasion of the fiber with the finishing agent applicator. The spinning tension is a value that divides the yarn tension (cN) measured in a separate position downwardly from the finishing agent applicator 13 in Figure 11 by approximately 10 cm by the yarn fineness (dtex) of the fiber conjugate on the pick up roller. The spinning tension is suitably adjustable according to the filament yarn collection methods. For example, the spinning tension can be adjustable according to the spinning speeds, the distance from the spinneret to a position at which the yarn is collected and the kinds of picking guides. The agent application of - -
The finishing is preferably carried out simultaneously with the collection of the filament yarn. In the production method according to the present invention, it is important that the coiled or wound coil is maintained at a temperature of 30 ° C or less. By maintaining the temperature of the coil wound to 30 ° C or less, it is possible to eliminate the high edge shape of the coil or the drawbacks of the fiber in the edge portion of the coil due to the shrinkage of the conjugate fiber. If the coil temperature exceeds 30 ° C, the coefficient of variation of the yarn fineness variation period becomes greater than 0.4 even if the yarn fineness variation value U% is suppressed to a value as low as possible. , so that the objective of the present invention can not be obtained. This fact has been found for the first time by the present inventors and is one of the important features of the present invention. Since the temperature of the coil during winding exceeds about 40 ° C in the high speed winding of the prior art, the drawbacks of the fiber in the edge portion have not been eliminated. The temperature of the coil is preferably maintained at 30 ° C or less from the start to the end of the winding operation. One way to maintain a coil temperature of 30 ° C or less, is by heat conduction and heat radiation from a motor which is a driving source of the coil and the source of heat generation for the coil shaft and is intercepted preferably. In addition, the wound coil and the area surrounding it are preferably cooled with cooling air to obtain the above objective. The coil temperature during the winding is preferably as low as possible. More preferably about 25 ° C or less. Since a large amount of energy is required to maintain an excessively low temperature, the temperature of the coil is most preferably in a range of about 20 to 25 ° C. According to the production method according to the present invention, the winding speed is in a range from 1500 to 4000 m / min, preferably from 1800 to 3500 m / min, and more preferably from 2000 to 2300 m / min. min. If the winding speed is within the above range, the degree of orientation of the conjugate fiber that is spun is sufficiently high and the value U% of fineness variation of yarn as well as the coefficient of variation of yarn fineness are within the range defined by the present invention. In addition, since the spinning tension and the stretching tension are not retained in the wound fiber, the difference in the value of dry heat shrinkage tension between the edge portion and the central portion of the coil is 0.05 cN / dtex or less to obtain the objective of the present invention. When a heat treatment is carried out during the winding process, the tension is maintained at 0.02 cN / dtex or more to minimize the variation of yarn fineness, so that no thread or lint ruptures are generated, although the temperature of heat treatment exceeds 70 ° C. Next, conditions peculiar to the method for making a pre-oriented conjugate fiber coil of polyester type according to the present invention will be described below. In Figure 11, the conjugate fiber captured by the first drawing roller 14 is wound as a coil 16 of conjugated fiber preoriented by means of a second drawing roller 15 without substantially stretching. At least one of a first stretching roller 14 and a second stretching roller 15 are preferably heated like a hot drawing roller so that the preoriented conjugate fiber is heat treated before being wound on the bobbin. The heat treatment is not limited to only that which uses the hot drawing roller but can be carried out by any method with the condition that the fiber can be heat treated before being wound on the coil.
The heat treatment condition for the preoriented conjugated fiber is preferably that wherein the heat treatment temperature is in a range of 70 to 120 ° C and the heat treatment stress is in a range of 0.02 to 0.1 cN / dtex . The heat treatment is preferably carried out by wrapping the pre-oriented conjugate fiber 2 to 10 times around a hot drawing roller. In this case, the temperature of the hot drawing roll is preferably maintained at a level generally equal to the heat treatment temperature of the pre-oriented conjugate fiber. If the heat treatment temperature is 70 ° C or higher, the calorific value of crystallization of the resulting pre-oriented conjugate fiber is 10 J / g or less so that the objective of the present invention can be obtained more efficiently. When the heat treatment temperature exceeds 120 ° C, the vibration of the yarn becomes significant in the drawing roller because the pre-oriented conjugate fiber having a low degree of crystallization abruptly comes into contact with a high temperature which causes the generation of lint or thread breakage, so it is difficult to maintain a stable production. In addition, the U% value of yarn fineness variation of the resulting pre-oriented fiber exceeds 1.5%. In this way, the heat treatment temperature preferably is in a range of 80 to 110 ° C, more preferably 90 to 110 ° C. The heat treatment stress of the preoriented conjugate fiber is measured in the hot drawing roll or in a position directly after it leaves the hot drawing roll. The adjustment of this tension is carried out by regulating the temperature and the speed of the hot drawing roller. If the heat treatment stress is within the above-mentioned range, the vibration of yarn in the drawing roller is minimized and the displacement of the pre-oriented conjugate fiber becomes stable. Also, there is no tight winding of the coil. The tension by heat treatment is preferably in a range of 0.03 to 0.07 cN / dtex. Although there is no limitation on the heat treatment time, a range of approximately 0.01 to 0.1 seconds is generally used. Next, conditions peculiar to the method for producing the stretched conjugate fiber coil of polyester type, according to the present invention will be described below. In Figure 11, when the stretched conjugate fiber coil of polyester type is produced, the conjugate fiber captured by the first drawing roller 14 is continuously drawn by the second drawing roller without being wound once in a coil and then coiled by the winder to form a predetermined drawn conjugate fiber coil 16. During drawing, the temperature of the first drawing roller 14 is preferably maintained in a range of 50 to 90 ° C, and more preferably 55 to 70 ° C. The second drawing roller 15 is heated so that the drawn yarn is heat treated by a second drawing roller 15. The heat treatment temperature preferably is in a range of 90 to 160 ° C, more preferably 100 to 140 ° C. In the present invention, it is necessary that the stretching tension be in a range of 0.05 to 0.40 cN / dtex, preferably of 0.10 to 0.30 cN / dtex. If the drawing tension is within the above range, the drawn conjugate fiber of polyester type has a sufficient tensile strength of about 1.5 cN / dtex. In addition, the elongation at break of the same is 30% or greater so no lint or yarn breakage will occur during the stretching. The drawing tension is defined by a ratio of speed between the first drawing roller 14 and the second drawing roller 15. The stretching tension is determined by selecting the combination of a ratio in the peripheral speed between the first and second drawing rollers ie a stretching ratio; and the temperature of the first drawing roller. When the first drawing roller has a speed in a range of 1500 to 3000 m / min and a temperature in a range of 50 to 90 ° C, a drawing tension can be obtained in a favorable range by adjusting the drawing ratio to a value in a range of 1.4: 5 times. The stretching ratio is preferably in a range of 1.4 to 2.0 times. According to a known direct spinning / stretching method, the stretching tension reached is as high as approximately 0.5 cN / dtex or higher when the stretching ratio is in a range of 3 to 5 times. On the contrary, according to the present invention, the drawing is carried out at an additional low drawing tension. In the present invention, the peripheral speed
VR of the second hot drawing roller 15 preferably is in a range of 2000 to 4000 m / min, more preferably from 2400 to 3300 m / min. If the peripheral speed VR is within the above range, it is possible to cause the first drawing roller to rotate at a peripheral speed of 1500 m / min or higher, whereby the vibration of the filament yarn becomes small to stabilize the yarn displacement during spinning and stretching. In addition, since the shrinkage of the stretched conjugate fiber of the polyester type is minimized during winding or after having been wound on a coil, the height of the edge portion of the coil is low to reduce the voltage fluctuation when the fiber is unwound from the coil at high speed. In the present invention two or three pairs or more of drawing rollers are used. A pair of pretensioning rollers can be provided in front of the pick-up drawing roller. One suitable apparatus for producing the stretched conjugated fiber of polyester type is that having three pairs of drawing rollers, as shown in Figure 12. A third stretching roller 17 can be heated or unheated. However, the hot drawing roller is preferable for the purpose of obtaining a dry heat shrinkage tension value in a range of 0.02 to 0.24 cN / dtex from the stretched conjugated fiber of polyester type and to facilitate stretch elongation CE2 of the same. When a third hot drawing roller is used, the temperature thereof is in a range of 50 to 180 ° C, more preferably 90 to 150 ° C. If the temperature is within this range, the winding is carried out in a stable state without the occurrence of thread breakage. In the present invention, heat setting is carried out between the second drawing roller 15 and the third drawing roller 17 under tension in a range of 0.05 to 0.5 cN / dtex, it is possible to produce a stretch elongation CE2 as high as 5. % or older. The tension between the second drawing roller 15 and the third drawing roller 17 can be determined by a ratio of speed between them. The speed ratio between the second and third drawing rollers is preferably in a range of 1.0 to 1.1. In the present invention, the winding is preferably carried out so that the VW / VR ratio satisfies the following formula (2): 0.85 < VW / VR < 1 (2) where Vw is a winding speed and VR is the speed of the second hot drawing roller. To help understand the formula (2), Figure 13 shows a favorable area in relation to VR and Vw R. In Figure 13, a horizontal axis represents the speed VR of the second drawing roller and the vertical axis represents the proportion VW / VR. That is, the speed ratio VW / VR means a relaxation ratio from the second drawing roller to the winder. In the present invention, the VW / VR ratio is preferably 0.85 or greater. If the VW / VR ratio is less than 0.85, the tension decreases between the second drawing roller and the winder, which can alter a stable winding. The VW / VR ratio is preferably in a range of 0.90 to 0.96. In the present invention, the winding is preferably carried out by satisfying the formula (2) at a rate of speed such that the winding tension between the second drawing roller 15 and the winder in Figure 11 or between the third drawing roller and the The winder in Figure 12 is preferably in a range of 0.02 to 0.12 cN / dtex, more preferably 0.04 to 0.07 cN / dtex. If the winding tension is within the above range, a high-end shaped coil or a dented coil does not result. According to the production method of the present invention, the transverse angle is preferably changed. in a range of 3 to 10 degrees, more preferably from 4 to 9 degrees from the start of completion of the coil formation, according to the respective winding diameters of the coil. If the transverse angle is within the above range, collapse does not occur so that a normal shaped winding can be obtained, free of a high shore portion. The transverse angle is determined by adjusting the winding speed and the transverse speed.
In the present invention, the transverse angle in the middle yarn layer of the spool is preferably greater than that of the innermost yarn layer. In this regard, the innermost yarn layer of the bobbin is a layer that exists within a thickness of about 10 mm from the surface of the bobbin. According to the most favorable aspect to change the transverse angle according to the winding diameters, the transverse angle is small at the beginning of the winding; that is, in the innermost thread layer of the coil; and it increases gradually as the winding diameter increases until a maximum value is reached in the middle yarn layer, after which the transverse angle is again reduced in the outermost yarn layer. By changing the transverse angle according to the winding diameter in this manner, it is possible to minimize both the dents and a high edge of the coil. The winding method mentioned before the yarn, while changing the transverse angle according to the winding diameters, is also applicable to the method for producing the pre-oriented conjugated fiber of the polyester type described above, and results in a favorable effect. It will be described a. then a method for producing false twist textured yarn of the conjugated figure of polyester type according to the present invention. This method is more effective for a false twist texturing process of the pre-oriented conjugated fiber of the polyester type. In the present invention, when the pre-oriented polyester type conjugate fiber in the coil is subjected to the false and stretched twist texturing process or the pre-oriented conjugate fiber of polyester type in the coil is subjected to a false twist texturing process , the coil temperature is maintained at 30 ° C or less, preferably 25 ° C or less, throughout the entire process including winding, storage and false twist texturing. If the temperature is within the above range, there is no high edge in the coil during the period from storage until the texturized by false twist so that a yarn texturized by false twist excellent in terms of appearance quality can be obtained. The false twist texturing process can be of a conventional type such as the type of bolt, the type of friction, the type of belt narrowing or the type of air torque. Although the false twist texturing heater may be of the single heater type or dual heater type, the first type is favorable for the purpose of obtaining a high susceptibility to drawing. The temperature of the heat is determined so that the yarn temperature reaches 130 to 200 ° C, preferably 150 to 180 ° C, and more preferably 160 to 180 ° C, measured at a position directly after the output of the first heater. The false twist texturing heater can be of contact type or non-contact type. The stretch elongation CE2 of the false twist textured yarn obtained by the single torsion type false twist texturing process preferably is in a range of 50 to 250% and a stretching modulus preferably of 80% or greater. If necessary, a second heater can be used to adjust the heat to obtain a false twisted texturized yarn of double heater type. The temperature of the second heater is preferably in a range of 100 to 210 ° C, more preferably in a range of -30 to + 50 ° C in relation to the temperature of the yarn measured in a position directly after the exit of the first Heater. A supercharging ratio in the second heater (a second supercharging ratio) is preferably in a range of + 3% to + 30%.
The false twist textured yarn of the polyester type conjugate fiber in the coil of the invention has good appearance and is free from dyeing irregularities and is excellent in terms of drawing susceptibility and shape recovery properties after drawing. For example, the stretching elongation of the apparent corrugation, which is visible before being treated with boiling water, is in a range of 50 to 300%. It is important that the fiber has a visible big ripple visible before being treated with boiling water, to obtain an excellent fabric in terms of recovery of elongation; that is, susceptibility to stretching and instant recovery; because such fiber can develop remarkably curls, by treatment with boiling water, even if it is used in a fabric having a high restraining force such as a woven fabric. If the false twist textured yarn of the polyester type conjugate fiber obtained by the present invention is used for a weft yarn, a gray fabric before being treated with boiling water also has the susceptibility to stretching similar to that of a resultant woven fabric. This property has never been observed in a conventional woven fabric in which known false twisted texturized yarn or a latent crimped conjugate fiber is used. The false twist textured yarn of the polyester type conjugated fiber obtained by the present invention has a stretch elongation CE2 measured under a load of 2 x 10-3 cN / dtex after being treated with boiling water in a range of 50 to 250% and shows a ripple development property, which is one of the features of the present invention. It will be understood that the false twisted texturized yarn according to the present invention exhibits an extremely high crimping performance as compared to the fact that a known false twisted texturized yarn obtained by means of false twist texturing of a conventional fiber consisting of Only PTT has a stretch elongation of approximately 30%. In addition, another feature of the polyester-type conjugate fiber is that the elongation recovery rate, after it is treated with boiling water, is in a range of 20 to 50 m / sec, which is an excellent test. Instant recovery The drawing recovery speed is measured in such a way that, after the textured yarn - by false twisting of the conjugated fiber of the polyester type - is treated with boiling water without subjecting it to load, the curling thereof is stretched until the tension reaches a predetermined value, after which the fiber is cut and the speed at which the fiber returns to its original length is measured. The greater the recovery speed of stretching, the faster the stretch recovery of the fabric; that is, it is more suitable in terms of adaptability to body movements when using the yarn for fabrics and for clothing. If the stretch recovery speed is 15 m / sec or more in the knitted fabric and 20 m / sec or more in the woven fabric, an excellent fabric can be obtained in terms of adaptability to the movements of the body. If the stretch recovery rate is less than this value, the adaptability to body movements becomes insufficient when the yarn is knitted or woven into a fabric. The drawing recovery speed is preferably 20 m / sec or greater in the knitted fabric and 25 m / sec or greater in a woven fabric. As is evident from the fact that the drawing recovery speed of a known spandex elastomeric fiber is in a range of about 30 to 50 m / sec, it will be understood that the false twisted texturized fiber of the conjugate fiber of the type polyester according to the present invention has a stretch recovery as good as an elastomeric Spandex type fiber. In this regard, it is difficult, with the current technical level, to produce a fiber having a draw recovery speed of 50 m / sec or greater. The drawing recovery speed of a false twisted texturized yarn of the known PET type is about 10 m / sec, and that of a twisted yarn textured yarn of a fiber consisting solely of PTT is about 15 m / sec. sec. The measurement of the drawing recovery speed described in the above has been invented by the present inventors, and the recovery property after the stretch has been measured quantitatively for the first time. A fabric obtained by the use of conjugate fiber of polyester type according to the present invention which is not subjected to a false twist texturing process is also free from irregularities of periodic dyeing and has a good appearance quality as well as softness and touch The conjugated fiber of polyester type according to the present invention can be used to form the whole of a fabric, or it can be mixed with other fibers and used to make it part of the fabric. The other fibers to be mixed with the present are, for example, polyester fiber, cellulose fiber, nylon 6 fiber, nylon 66 fiber, acetate fiber, acrylic fiber, polyurethane elastomer fiber, wool or silk It includes a type of filament and a type of short fiber, but it is not limited to these. To obtain a mixed fiber composite yarn by mixing or combining the conjugated fiber of polyester type according to the present invention with other fibers, various methods can be used.; for example, a method in which the fiber of the invention is intertwined-mixed with other fibers; a method in which the interlaced-mixed fibers are textured by false twist and stretched; a method in which one of the fibers is textured by false twisting and subsequently interlaced-mixed with another; a method in which both fibers are textured by false twisting, separately and then joined by interlacing-mixing; a method in which one of the fibers is subjected to Taslan processing and subsequently interlaced-mixed with another; and a method in which both fibers are subjected to Taslan mixing. The mixed fiber composite yarn obtained by the above methods preferably has interlaced portions of 10 dots / m or greater.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic illustration of an example of a coil having no high shore portion; Figure 2 is a schematic illustration of an example of a coil having a high shore portion, wherein the reference numerals are as follows: 18: spool used for the winding, 19: conjugate fiber coiled; 20: high edge portion,: winding diameter, H: winding width; A: winding width of the innermost layer of the bobbin, B: winding width when the yarn layer 'has a predetermined thickness, T: winding thickness, a: bore diameter, ß: diameter of the central portion and f; a transversal angle. Figure 3 is an example of a measurement diagram of the value U% of yarn fineness variation; Figure 4 is another example of a measurement diagram of the value U% of yarn fineness variation; Figure 5 is an example of a yarn fineness variation period analysis diagram; Figure 6 is another example of a yarn fineness variation period analysis diagram; Fig. 7 is an example of an unrolling tension jitter diagram;
Fig. 8 is another example of an unwinding tension jitter diagram; Figure 9 is a diagram showing a favorable area of the difference in unwinding tension and unwinding speed, according to the present invention; Figure 10 is a schematic illustration of an example of a row used in the present invention; wherein the reference numbers are as follows: a: distributor, b: spin hole; D: hole diameter, L: hole length, T: tilt angle, P: polymer supply hole, and Q: hole in. polymer supply; Figure 11 is a schematic illustration of an example of a method for producing a conjugate fiber coil; Figure 12 is another schematic illustration of an example of a method for producing a conjugate fiber coil; and Figure 13 is a diagram showing a favorable area of the winding condition according to the present invention. In Figure 11 and Figure 12, the reference numbers are as follows: 1: dryer, 2: extruder, 3: dryer, 4: extruder, 5: fold, 6: fold, 7: thread head, 8: coil thread, 9: row, 10: filament, 11: blowing area without air, 12: cooling air, 13: finishing agent applicator, 14: first drawing roller, 15: second drawing roller, 16: fiber coil conjugate: 17: third drawing roller.
BEST MODES TO CARRY OUT THE INVENTION
The present invention will be described in greater detail in the following when referring to the examples, but should not be considered to be limited thereto. In this regard, the measurement methods or quantification methods are as follows: (1) Intrinsic viscosity The intrinsic viscosity [?] Is a value determined by the definition represented by the following formula: [?] = Lim (nr - 1 ) / C c > 0 where 'nr is a value that is obtained by dividing the viscosity of a diluted solution of the polymer dissolved in o-chlorophenol having a purity of 98% or more, by a viscosity of the previous solvent measured at the same temperature, which is defined as the relative viscosity. C is the concentration of polymer represented in g / 100 ml.
(2) Difference in winding diameter of the coil. The winding diameter a of the edge portion and ß of the central portion, which are shown in Figure 2, are measured, from which the difference in winding diameter is obtained by the following formula: Difference in diameter winding (mm) = a - ß (3) Dent percentage The winding width A of the innermost yarn layer of the bobbin and the B value of a yarn layer in a winding thickness T / 2 are measured when you have a total winding thickness T that is shown in figure 2, from which the percentage of dent is obtained by the following formula: Dent percentage (%.}. = [(B - A) / A] xl00 (4) Winding hardness By using a hardness determiner. (GC type-A) available from Techrock K., the hardness is measured at opposite shore portions of the conjugate fiber coil, respectively, at four points 90 degrees apart from each other in the circumferential direction, and the average value of the The hardness of the edge portion is measured at a point 2 mm away from the lateral end surface. (5) Difference in unwinding tension The unwinding tension is recorded in a diagram while The conjugate fiber is unwound from the conjugate fiber coil at a speed of 1000 m / min.The voltage measurement is carried out by using a voltage meter (ODEL-1500) available from EIKO SOKKI KK The respective continuous measurement for 60 seconds and the voltage fluctuations are recorded in a diagram, from which the fluctuation width (g) of the unwinding tension is read and divided by the yarn fineness (dtex) of the conjugate figure to obtain the difference in unwinding tension. (6) Elongation at break The elongation at break is measured according to JIS-L-1013. (7) Tension value at 10% elongation. The tension value is measured at 10% elongation according to JIS-L-1013. The tension and elongation of the conjugate fiber is measured 100 times in the direction of the length of the wire, from which the tension (cN) at 10% elongation is obtained. The maximum values and the minimum value are read in the measured values, from which the difference is obtained and divided between the yarn fineness (dtex) which results in a tension value at 10% elongation (cN / dtex).
(8) Heat Shrink Voltage Value A thermal stress measuring device (eg KANEBO ENGINEERING K.K. KE-2) is used to determine the heat shrink stress value. The conjugated fiber is cut into pieces 20 cm long, the opposite ends of which are held together to form a loop. This test piece is mounted on a measuring device and the shrinkage stress is measured by heat under an initial charge of 0.044 cN / dtex at a rate of temperature increase of 100 ° C / min. The variation of shrinkage stress by heat according to the temperature is recorded in a diagram. The temperature at which the shrinkage voltage is generated, that is, a temperature at which the voltage increases from a basal value, appears in the diagram; which is obtained and is referred to as heat shrink stress development temperature. The heat shrink stress shows a hill-like curve with a high temperature area. A maximum voltage value (cN) is read and the heat shrink tension value is obtained by the following formula: Heat shrink stress value (cN / dtex) =. { maximum voltage value (cN) / 2} /. { Thinness of the thread (dtex)} - initial load (cN / dtex) (9) Thinness variation of the wire A diagram of the fineness variation value of the wire (mass diagram) is obtained by the following method and the U% value is measured simultaneously with it. Measuring device: uniformity determiner (manufactured by Uster Zellweger Co,: Uster tester UT-3) Measurement conditions: Wire speed: 100 m / min Tension strength: 12.5% Voltage adjustment: 1.0 Input pressure: 2.5 hp Twist: Z; 1.5 T / m - Measured thread length: 250 m / min Scale: corresponds to the variation of fineness of the thread. The value U% variation of yarn fineness is read directly: the variation diagram and the value of the diagram. Coefficient of variation of yarn fineness: a period analysis diagram (mass spectrogram, a diagram of variance periodicity in the fineness variation of CV yarn) is obtained by using a fineness variation period analysis software of yarn belonging to the measuring device, from which a height of a projected signal is measured; that is, the coefficient of variation. (10) Fiber-fiber dynamic friction coefficient The 690 m long fiber is wrapped around a cylinder under a tension of approximately 15 g at a transverse angle of 15 degrees. Then the same kind of fiber as in the previous 30.5 cm is hung on the cylinder while vertically crossing the cylinder axis. A load (g) corresponding to 0.04 times the total yarn fineness of the fiber hung on the cylinder is attached to one end of this fiber and a tension gauge is connected to the other end thereof. Subsequently, the cylinder is rotated at a peripheral speed of 18 m / min and the voltage is measured by the voltage gauge. From the tension obtained in this way, the coefficient of fiber-fiber dynamic friction, f, is determined by the following formula. f = (1 /?) x ln (T2 / T1) where TI is the weight (g) applied to the fiber, T2 is an average voltage (g) of at least 25 measured values, ln is the natural logarithm and ? is the radius of the circumference of the circle with respect to its diameter. In this regard, the measurement is carried out at 25 ° C. The measurement of the coefficient is carried out ten times in groups of fibers with a weight of 100 g, and the difference between the maximum and minimum values in the direction of yarn length is obtained. (11) Stretch elongation (Ve) before being treated with boiling water. A skein is formed by winding the yarn around a bob that has a circumferential length of 1125 m, ten times. A load of 2 x 1CT3 cN / dtex is applied immediately to it, and after 30 seconds the length (Ll) of the skein is measured. The load is then removed from 2 x 10"3 cN / dtex and a new load of 0.18 cN / dtex is applied, after which a length (L2) of the skein is measured after 30 seconds, the stretch elongation is obtained (Ve) by the following formula: Stretch Elongation (Ve) = [(L2 - Ll) / Ll] xlOO
The measurement is repeated ten times and the average value is obtained. (12) Stretch elongation (CE2) A skein is formed by winding the yarn around a bob that has a circumferential length of 1125 m ten times, and heat treated in boiling water for 30 minutes under a load of 2 x 10"3 (cN / dtex) The skein is then dried by dry heat at 180 ° C for 15 minutes under this load After the treatment, the skein is kept stationary in a static thermo-humidity chamber defined by JIS-L-1013 a full day and night, without loading, then the skein is loaded with 0.18 cN / dtex for 30 seconds and the length (L4) of the skein is measured, then the load is removed from 0.18 cN / dtex and a new load of 1 x 10"3 cN / dtex is applied. After 5 minutes the length (L3) of the wood is measured. Stretch elongation is obtained from the following formula: Stretch Elongation (CE2) = [(L4 - L3) / L3] xl00 The measurement is repeated ten times and the average value is obtained. (13) Calorific value of crystallization A differential heat calorimeter of heat flux type (DSC-50) manufactured by SHIMADZU SEISAKUSHO K.K. 5 mg of the preoriented conjugated fiber to be measured is accurately weighed and differential scanning calorimetry (DSC) measurement is carried out in a range of 25 to 100 ° C at a temperature increase rate of 5 ° C / min. The calorific value of crystallization is obtained by calculating the area of heat generation peaks developed in a region of 40 to 80 ° C in the DSC diagram by using a program belonging to the differential scanning calorimeter.
(14) Twisted yarn stretching module for false twisting The measurement is carried out according to the method JIS-L-1090 to test the stretchability susceptibility (A). (15) Recovery speed of elongation A skein is formed by winding textured yarn subjected to false twisting around a bobbin having a circumferential length of 1125 m, ten times, and treated with boiling water for 30 minutes without subjecting it to load. The measurement is carried out on it in accordance with JIS-L-1013 as follows: The yarn textured by false twisting treated with boiling water is left stationary one day and one night, without charge. The twisted yarn is stretched by a voltage determinant until the tension reaches 0.15 cN / dtex and is maintained in this state for three minutes. The thread is then cut with scissors in a position directly above the lower narrowing point. The shrinkage speed of the textured yarn is measured by false twisting cut with the scissors when using a high-speed video camera (resolving power: 1/1000 sec) as follows. A ruler with millimeter scale parallel to the textured yarn is fixed by false twisting at a distance of 10 mm. Recovery of a front end of the cut wire is taken by the video camera while focusing the front end. The record of the video camera is played to read the displacement
(mm / msec) from the front end of the textured yarn by false twisting and the recovery speed is obtained
(m / sec). (16) Coil temperature The coil temperature is measured during winding by using a non-contact type thermometer (THERMOVIEWER: JTG-6200 TYPE) manufactured by NIPPON DENSHI (JEOL) K.K. (17) Spinning tension Using a ROTHSCHILD Min Tension R-046 tension meter, a TI (cN) tension applied to a moving fiber is measured at a position 10 cm below the people's applicator nozzle of finishing (reference number 13 in figures 11 and 12). The measured tension is measured between the fineness of fiber D (dtex) to obtain a spinning tension. Spinning tension (cN / dtex) = Tl / D (18) Heat treatment stress Using a ROTHSCHILD Min Tens R-046 tension meter, the tension T2 (cN) applied to a fiber in displacement during the heat treatment at the exit of a hot drawing roller (between the first drawing roller 14 and the second drawing roller 15 in FIG. 11) is measured. The measured tension is divided by the fineness of the fiber D (dtex) of the drawn fiber to obtain a heat treatment stress. Heat treatment stress (cN / dtex) = T2 / D (19) Stress tension Using a ROTHSCHILD Min Tens R-046 tension meter, measure the tension T3 (cN) applied to a fiber during displacement the drawing, in a position between a supply roll and a heat treatment device (between the first drawing roll 14 and the second drawing roll 15 in Figure 12). The measured tension is divided by the fineness of the fiber D (dtex) of the drawn fiber to obtain a heat treatment stress. Stress tension (cN / dtex) = T3 / D (20) Fluctuation in the unwinding tension. The unwinding tension is recorded in a diagram while the conjugate fiber is unwound from a conjugate fiber coil at a speed of 1000 m / min. A voltage meter (MODEL 1500) manufactured by EIKO SOKKI .K is used. for voltage measurement.
Each measurement lasts 60 seconds and is recorded in a diagram. For this diagram, a width (g) of the unwinding tension fluctuation is read and divided by the fineness of the fiber of the conjugate fiber to obtain a difference in the unwinding tension. (21) Unwinding property and false torsional capacity The false twisting texturing is carried out under the following condition, in which the number of yarn ruptures per day is obtained when it is carried out continuously texturized by twisting in false by a 96 spindle / machine false twist machine. The machine of texturized of torsion in false: machine of type 33H (type of band) manufactured by MURATA KI AI SEISA ÜSHO K.K. Conditions of false torsion: Thread speed: 500 m / min Number of false twists: 3230 T / m First supply ratio: -1% First heater temperature: 170 ° C 1) Unwinding property Number is counted of yarn breaks that occur between stretched reel at the entrance of the feed roller, based on which a judgment is made according to the following criteria: the yarn rupture is less than 10 times / day per machine; .- very good OR the breaking of the thread is in a range of 10 to 30 times / day per machine; good X thread breakage exceeds 30 times / day per machine, making industrial production difficult. 2) False torsional capacity The number of yarn ruptures that occur in a heater after a feeding roller is counted, based on which the judgment is made according to the following criteria: the yarn rupture is less 10 times / day per machine; : very good OR the breaking of the thread is in an interval of 10 to 30 times / day per machine; good X thread breakage exceeds 30 times / day per machine, making industrial production difficult. (22) Dyeing appearance quality A flat wavy fabric is prepared by using stretched PTT yarn (manufactured by ASAHI KASEI KK; "Solo") of 56 dtex / 24f as warp yarns distributed with a warp density of 72 warp / 2 and the conjugate fiber of polyester type as weft yarns at a screen density of 80 ends / 2.54 cm, and washed thoroughly and dyed in the usual manner. The quality of appearance of the resulting fabric is determined by an expert, according to the following criteria: very good because there is no irregularity in the periodic dyeing; Or good because there is no irregularity in the periodic dyeing X bad because there is irregularity in the periodic dyeing or staining (23) Stability of spinning The spinning by melting and stretching are carried out for two days in each of the examples by using a spinning spinning machine that has a row of four ends per spindle. From the number of times of thread breakage in this period and the frequency of generation of lint in the resulting drawn yarn bobbin (a proportion of the number of bobbins in which lint was generated), the yarn stability of according to the following criteria: S there is no breakage of the thread and the proportion of the number of coils having fluff is 5% or less OR the thread break is twice or less and the proportion of fluff generated in the coil is less than 10% X the thread break is three times or more and the proportion of fluff generated in the coil is 10% or greater. (24) Total calculation The total unrolling property, susceptibility to processing and dyeing appearance quality is determined, according to the following criteria: • f the entire unwinding property, susceptibility to processing and appearance quality of dyed are very good. Or: the unwinding property, processing susceptibility and dyeing appearance quality are good, or at least one of them is very good. X at least one of the unwinding property, processing susceptibility and dyeing appearance quality is not good.
[Examples 1 to 5] In these examples, the production of the preoriented conjugate fiber coil type polyester will be described, that is, the effect of the heat treatment conditions on the physical properties of the preoriented conjugate fiber will be described and- the shape of the coil. A pre-oriented conjugate fiber of PTT type of 70 dtex / 24 filaments is produced by using a spinning machine and the winder shown in Figure 11 from PTT pellets having an intrinsic viscosity of 1.2 dl / g and they contain 0.4% by weight titanium oxide as a component, and PTT pellets having an intrinsic viscosity of 0.92 dl / g and containing 0.4% by weight titanium oxide as another component. The spinning conditions are as follows: Pellet drying temperature and final moisture content: 110 ° C, 15 ppm Extruder temperature: arrow A: 255 ° C and arrow
B: 250 ° C: Thread head temperature: 265 ° C Spinning hole diameter: 0.35 mm f Spinning hole length: 1.05 mm (L / D = 3) Spinning hole inclination angle T: 35 degrees Cooling air: temperature of 22 ° C, relative humidity of 90%, speed of 0.5 m / sec Finishing agent: aqueous emulsion consisting mainly of polyether ester (a concentration of 10% by weight) Distance from the row to the finishing agent applicator nozzle: 75 cm · Spinning tension: 1.3 cN / dtex (Condition of winding) First draft roller: speed 2300 m / min; temperature as described in table 1. Second draft roller: speed of 2400 m / min; without heating Winder: AVI-909 manufactured by TEIJIN SEIKI K.K.
(both axes of a reel and the contact roller are self-propelled) Winding speed: 2420 m / min Winding coil temperature: 25 ° C Winding is carried out while changing the temperature of the first stirrer roller, as shown in Figure 1. The shape of the coil and the physical property of the PTT-type pre-oriented conjugate fiber are the following: (Pre-oriented conjugate fiber coil) Moisture content: 0.6% by weight Winding diameter: 310 mm Width of winding: 100 mm Length of the thread between a portion of the edge with respect to the opposite portion: 90 cm Winding weight: 5.2 kg / coil Physical properties of the pre-oriented conjugate fiber Average intrinsic viscosity [?] 1.02 Fiber fineness: 69.4 dtex Strength : 1.7 cN / dtex Elongation: as described in table 1 Coefficient of fiber-fiber dynamic friction: 0.28 Difference in the coefficient of dynamic friction in the direction of wire length re the maximum and minimum values: 0.03 Difference in tension at 10% elongation between the maximum and minimum values: 0.11 cN / dtex Interlacing degree: 4 points / m (Physical properties of a yarn textured by false twisting) Fineness of the thread; 56.0 dtex Strength: as described in table 1 Elongation: 36% Stretch elongation: 300% Stretch elongation CE2 under a 2 mg load: as described in table 1 Stretch recovery speed: 29 m / sec difference in unwinding tension in table 1 is measured at an unwinding speed of 1000 m / min. The quality of dyeing appearance of the woven fabrics obtained by the use, as weft yarns, yarns textured by false twisting that results from the conjugate fiber coils produced by these examples is shown in table 1. As is evident from the Table 1, the resulting woven fabric is free of the periodic drawback caused by the edge portion of the coil and is excellent in terms of dye uniformity and also has a high stretch elongation and shape recovery property after stretching.
[Examples 6 to 10 and Comparative Examples 1 and 2] In these examples, the effect of the winding speed in the winding condition on the production of a pre-oriented conjugate fiber coil of the PTT type will be described. These examples are carried out in the same manner as in example 1, except for the conditions shown in table 2. The heat treatment is carried out under the condition where the first drawing roller is heated to 80 °. C and the second drawing roller is not heated; and the heat treatment stress (between the first and second drawing rolls in these examples) is 0.04 cN / dtex. A pre-oriented conjugate fiber coil of PTT type having the same coil size as in Example 1 is produced, but the winding speed is changed, as shown in table 2. In these examples and in the comparative examples the The temperature of the coil during the winding is maintained at 25 ° C.
The coil obtained from pre-oriented conjugate fiber of PTT type is stored for 30 days at 25 ° C and then subjected to the procedure of texturing by false twisting and stretching. Table 2 shows the quality of the dyeing appearance of textured yarns. The difference in the unwinding tension shown in table 2 is measured at an unwinding speed of 1000 m / min. As is evident from table 2, the woven fabric of the false twist textured yarn obtained from the pre-oriented conjugate fiber coil of the PTT type according to the present invention is free from irregularities of periodic dyeing, and also has a high stretching elongation and shape recovery properties after stretching.
[Examples 11 to 13 and Comparative Example 3] In these examples, the effect of the coil temperature during the winding in the production of a pre-oriented conjugate fiber coil of the PTT type will be described. These examples are carried out in the same manner as in Example 2, except that the cooling condition of the coiled PTT pre-oriented conjugate fiber coil changes as shown in Table 3.
Table 3 shows the shape of the resultant PTT-type pre-oriented conjugate fiber coil as well as the physical properties of the pre-oriented conjugate fiber. Table 3 shows the difference in unwinding tension, which is measured as an unwinding speed of 1000 m / min. As is evident from Table 3, the preoriented conjugate fiber coil wound to a temperature range of the present invention is excellent in the form of winding and the woven fabric obtained therefrom has good appearance quality.
[Examples 14 to 16 and Comparative Example 4] In these examples the effect of the spinning tension on the production of a pre-oriented conjugate fiber coil of PTT type will be described. These examples are carried out in the same manner as in example 2, except that the distance of the finishing agent applicator nozzle from the spinneret changes, as shown in table 4 to obtain a pre-oriented conjugate fiber coil of type PTT. Table 4 shows the susceptibility to spinning. The difference in the unwinding tension in table 4 is measured at an unwinding speed of 1000 m / min. As is evident from Table 4, when the spinning tension is within the range defined by the present invention, the spinning susceptibility becomes good and a false twist textured yarn with excellent appearance quality is obtained.
[Examples 17 to 21 and Comparative Examples 5 and 6] In these examples, the effect of the winding speed on the false twist capacity and the appearance quality · of the textured yarn when conjugate PTT pre-oriented fiber is coiled without having been heat treated during winding in the PTT pre-oriented conjugate fiber coil production. In addition, the effect of the storage condition of the PTT pre-oriented conjugate fiber coil will be described. Preturned conjugate fiber of PTT type of 71 dtex / 24 filaments is produced by using a spinning machine and the winder shown in figure 11 while changing the winding speed as shown in table 5 from pellets of PTT having an intrinsic viscosity of 1.25 dl / g and containing titanium oxide in 0.4% by weight as a component and PTT pellets having an intrinsic viscosity of 0.92 dl / g and containing titanium oxide in 0.4% by weight as another component. [Spinning condition] Pellet drying temperature and final moisture content: 110 ° C, 15 ppm Extruder temperature: arrow A: 255 ° C and arrow
B: 250 ° C. Thread head temperature: 265 ° C Thread hole diameter: 0.50 mm f Thread hole length: 1.25 mm Thread hole inclination angle T: 35 degrees Cooling air: 22 ° C temperature, relative humidity of 90%, speed of 0.5 m / sec Finishing agent: aqueous emulsion consisting mainly of polyether ester (a concentration of 10% by weight) Distance from the row to the applicator nozzle of the finishing agent. 75 cm (Condition of winding) Winder: A -909 manufactured by TEIJIN SEIKI K.K. (the arrows of both one coil and the contact roller are self-propelled) Winding coil temperature: 20 ° C (measured by a non-contact type thermometer) (Pre-oriented conjugate fiber coil) Moisture content: 0.6% by weight Winding diameter: 31 mm Width of winding: 19.3 cm Length of the wire between one edge portion to another: 90 cm Winding weight: 5.2 kg / bobbin (Physical properties of the pre-oriented conjugate fiber) Fiber-fiber dynamic friction coefficient: 0.26
Difference in the coefficient of dynamic friction in the longitudinal direction of the wire between the maximum and minimum values: 0.04 Difference in tension at 10% elongation between the maximum and minimum values: 0.09 cN / dtex Degree of interlacing: 9 points / m After the coiled pre-wound conjugate fiber coil is kept in an environment at 20 ° C and 90% relative humidity for five days until it is subjected to the false twist texturing procedure. Table 5 shows the shape of the preoriented conjugate fiber coil, the yarn fineness variation value of the unwound yarn from the bobbin, the false twist capacity and the quality of the dyed appearance of the textured yarn. . The unrolling tension difference in table 5 is measured at an unwinding speed of 1000 m / min. As is evident from Table 5, the PTT-type pre-oriented conjugate fiber coils obtained in Examples 17 to 21 of the present invention are excellent in their false and stretched torsional capacity and the textured yarns are good in terms of quality. Appearance of dyeing. The physical properties of the yarn textured by false twisting that is obtained by the texturing by false twisting and stretching of the yarn in the pre-oriented conjugate fiber coil is shown as follows: (Physical properties of yarn textured by twisting in false) Thread fineness : 56.6 dtex Resistance to traction; as shown in table 5 Elongation at break: 38% Stretch elongation: 243% Stretch elongation CE2 under a load of 2 mg: as shown in table 5. The twisted yarn with false twist has an elongation of stretched elevated Any of the instantaneous recovery speeds of the false twisted yarns in Examples 17 to 21 is 20 m / sec or greater, and the woven fabric is excellent in terms of dyeing appearance quality and shape recovery properties. after stretched.
[Examples 22 to 30 and Comparative Examples 7 to 9] In these examples the effect of temperature and time will be described to maintain a pre-oriented conjugate fiber coil of PTT type where the yarn has been wound without having been heat treated during the winding, and until it is carried out textured by false twisting. The PTT pre-oriented conjugate fiber coil is obtained according to the same spinning and winding conditions as in example 19 (in which the winding speed is 2400 m / min.) The PTT pre-oriented conjugate fiber coil obtained in this way it is obtained under the conditions shown in table 6 and subjected to false twist texturing .. Table 6 shows both the shape of the PTT pre-oriented conjugate fiber coil and the yarn fineness variation value measured while it is unwound from the spool, during the false twist texturing process as well as the false twist capacity and the dyeing appearance quality.
As is evident from table 6, when the yarn has been textured by false twisting and stretching after having been maintained within a temperature range defined by the present invention, the yarn has a favorable false twist capacity and the yarn Textured by false twisting is excellent in terms of quality of appearance of dyeing.
[Examples 31 to 35 and Comparative Examples 10 and 11] In these examples, the effect of the VW / VR ratio between the speed VR of the second hot drawing roller and the winding speed Vw in the production of the drawn conjugate fiber coil will be described. of polyester type. A PTT-type conjugate fiber coil of 84 dtex / 24 filaments is produced from PTT pellets having an intrinsic viscosity of 1.26 dl / g containing titanium oxide in 0.4% by weight as a component and PTT pellets. having an intrinsic viscosity of 0.92 dl / g containing titanium oxide at 0.4% by weight as another component by using a spinning machine and a winder having three pairs of drawing rollers, as shown in Figure 12. Spinning conditions in these examples are as follows: (Spinning conditions) Pellet drying temperature and final moisture content: 110 ° C, 15 ppm Extruder temperature: arrow A: 225 ° C and arrow
B: 250 ° C: Wire head temperature: 265 ° C Spinning hole diameter: 0.50 mm f Spinning hole length: 1.25 mm Spinning hole inclination angle T: 35 degrees Cooling air: temperature of 22 ° C, 90% relative humidity, speed 0.5 m / sec Finishing agent: 60% by weight aqueous fatty acid ester emulsion, 5% by weight polyether, 30% by weight nonionic surfactant and antistatic agent in 5% by weight (concentration of 10% by weight) Distance from the spinneret to the applicator nozzle of the finishing agent: 90 cm Spinning tension: 0.08 cN / dtex (winding condition) First draw roller: speed of 1500 m / min; temperature 55 ° C Second drawing roller: Temperature 120 ° C Third drawing roller: not heated Coiler: AW-909 manufactured by TEIJIN SEIKI .K. (both the arrow on the spool and the contact roller are self-propelled) Angle of travel: Winding thickness of 0 to 5 mm: 3.5 degrees Winding thickness of 5 to 70 mm: 6.5 degrees Winding thickness of 70 to 110 mm: 4.0 degrees Winding tension: 0.05 cN / dtex Coil temperature during winding: 25 ° C The winding is carried out while changing the speed VR of the second drawing roller as shown in table 7 so that the tension of the winding varies stretched. The shape of the coil and the physical properties of the resulting PTT stretched conjugate fiber are as follows: (Conjugate fiber coil) Moisture content: 0.6% by weight Winding diameter: 330 mm Outer diameter of the paper tube: 110 mm Width winding: 90 mm Winding weight: 5.2 kg / bobbin (Physical fiber property) Thread fineness; 83 · .5 dtex Average intrinsic thread viscosity [?]: 0.96 dl / g Interlacing degree: 7 points / m Fiber-fiber dynamic friction coefficient: 0.27 Difference in the coefficient of dynamic friction in the direction of yarn length between maximum and minimum values: 0.03 Difference in tension at 10% elongation between the maximum and minimum values: 0.14 cN / dtex The stretched conjugate fiber coil wound in this way is maintained in an environment at 30 ° C and 90% Relative humidity for 30 days. The property of 'unrolling the resultant drawn conjugate fiber coil as well as the physical properties of the drawn conjugate fiber are shown in Table 7. The difference in unwinding tension in Table 7 is measured at an unwinding speed of 1000. m / min Figure 7 shows a diagram of the fluctuation in the unwinding tension of the drawn conjugate fiber coil obtained in example 32 at an unwinding tension of 1000 m / min. As is evident from Table 7, if the difference in the dry heat shrink stress value of the drawn conjugate fiber and the difference in the unwinding tension are within a range defined by the present invention, the coil is excellent in Regarding unwinding properties and the resulting fabric is good in terms of quality of appearance of dyeing. In the comparative example 10 the susceptibility to spinning is worse because the drawing tension is low and the resulting fabric is inferior in terms of quality of appearance of dyeing. In comparative example 11, many fluffs were generated due to the high stretching tension. The resulting drawn conjugate fiber coil has a high edge portion that deteriorates the high speed unwinding property and the fabric is inferior in dyeing difference quality. The conjugate fiber stretched in Example 33 has been textured by false twisting by a false type 33H twisting texturing machine manufactured by MURATA KIKAI Co. (Condition of torsional texturing in false heater temperature Hl; 170 ° C Angle of Twisting: 110 degrees Stretching ratio: 1.16 Processing speed: 300 m / min (Physical properties of yarn textured by false twisting) Thread fineness: 71.0 dtex Strength or tenacity: 2.1 cN / dtex Elongation: 36% Stretch elongation: 290% Stretch elongation under a 2 mg load: 170% Elongation recovery speed; 25 m / sec. The textured and false twist textured yarn obtained by using the PTT-type stretched conjugate fiber coil of the present invention is excellent in terms of quality it is excellent in dyeing appearance quality and has a high stretch elongation and a shape recovery capacity after stretching.
[Examples 36 to 41 and Comparative Example 12] In these examples, the effect of the ratio of VW / VR between the speed VR of the second hot drawing roller and the winding speed Vw and the treatment with heat under tension, between the second and third hot drawing rollers, on the production of the PTT type conjugate fiber bundle. The drawn conjugate fiber coil is obtained by direct spinning and stretching in the same manner as in Example 31, except that the winding speed Vw is changed, as shown in Table 8. The winding condition is as follows: (Condition of winding) First drawing roller: speed of 2000 m / min, temperature of 55 ° C Second drawing roller: speed of 3045 m / min Proportion of drawing: 1.52 Drawing tension: 0.25 cN / dtex Second drawing roller: temperature of 120 ° C Speed ratio between the second and third draw rollers: as shown in Table 8. Third draw roller: temperature as shown in Table 8 The difference in unwinding tension in Table 8 is measured at a speed of unwinding of 1000 m / min. As is evident from Table 8, if the VW / VR ratio is within the range defined by the present invention, a stretched conjugate filter spool and a resulting fabric excellent in appearance quality is obtained. In addition, when the stretched conjugate fiber is heat treated by heating the third drawing roller, the stretching elongation CE2 becomes 20% or higher to develop a favorable curling susceptibility. In Comparative Example 12, the heat treatment is carried out at a rate of speed (third drawing roller / second drawing roller) of 0.98, which is a relaxed heat treatment, and the winding is a little stable because There is thread breakage during the winding.
[Examples 42 to 44 and Comparative Examples 13 and 14] In these Examples, the effect of the winding width of the conjugate fiber coil will be described. The conjugate fiber coils shown in Table 9 are obtained by melt spinning and continuous stretching in the same manner as in Example 33, while the transverse width of the coiler is differentiated during winding. Table 9 shows the winding weight and the shape of the conjugate fiber coil as well as the appearance quality of the resulting fabric. The difference in the unwinding tension in Table 9 is measured at an unwinding speed of 1000 m / min. In Figure 8 a diagram of the unwinding tension fluctuation is shown when the yarn is unwound from the conjugate fiber spool obtained in Comparative Example 14. As is evident from Figure 8, when the winding width of the coil is outside the range of the present invention, the voltage fluctuation is large at high unwinding speeds which deteriorates the unwinding properties. · As is evident from Table 9, if the winding width and the winding diameter of the conjugate fiber spool are within the range of the present invention, the result is that the unwinding properties are good and there is a cloth excellent in terms of appearance quality. For the purpose of showing the effect of the winding width of the conjugate fiber coil on the unwinding property, Table 10 shows the differences in unwinding tension at various unwinding speeds, related to a coil that is obtained in Example 32 and Comparative Example 14. As is evident from Table 10, the conjugate fiber coil of the present invention is excellent in its unwinding properties.
[Example 45] In this example, the effect obtained by changing the transverse angle according to the winding diameter will be described. The melt spinning and the stretching are carried out in the same manner as in Example 33, while changing the transverse angle according to the winding diameter, as follows: Transverse angle: - winding thickness from 0 to 10 rain: 4 degrees winding thickness from 10 to 70 mm: 7 degrees winding thickness from 70 to 110 mm: 4 degrees The resulting conjugate fiber coil has a diameter difference of 3 mm and the difference in unwinding tension is small as 0.002 cN / dtex, which results in a good unrolling property and dyeing appearance quality .
[Examples 46 and 47, and Comparative Example 15] In these examples the effect obtained by the changes in the polyester component used together with PTT as the other component will be described. When changing the polyester classes as the other component, conjugated fibers are obtained as shown in Table 11. Thus, in Table 11 the physical properties of the conjugate fiber coils obtained in this manner are shown. The difference in unwinding tension in Table 11 is measured at an unwinding speed of 1000 m / min. As is evident from Table 11, even if PET or PBT is used as the other component, a good unwinding property and good dyeing appearance quality is obtained. In Comparative Example 15 in which PET was used for both components, the stretch elongation CE2 of the stretched conjugate fiber and the stretch elongation CE2 of the textured yarn by false twist were low which shows inferiority in susceptibility to curling .
Table 1
Unrolled property? Torsional capacity in false ·
Quality of appearance of dyeing? · / O
Total rating or
Table 2
Table 3
Table 4
Table 5
? ? s? or ?? or
Table 6 TemperaPress of Difference in Difference in Value U% of Coefficient Capacity of Quality of Maintenance Rating the diameter value of variation of of variation twist in false appearance of total ion maintainers of winding texture fineness tension of fineness yarn of and stretched dyeing of the curling yarn by winding the coil shrinkage (%) yarn textured by the coil in false (mm) by dry heat twisting in false f weeks) < cN / dtex) Example 22 10 1 2 0.003 0.9 0.2 V · Example 23 10 2 2 0.003 0.9 0.2 | | /
Example 24 10 4 2 0.003 0.9 0.2 | ·
Example 25 20 l 3 0.004 0.9 0.2
Example 26 20 2 4 0.005 1.0 0.3
Example 27 20 4 5 0.005 1.0 0.3
Example 28 25 1 4 0.005 0.9 0.3 ·
Example 29 25 2 5 0.005 1.1 0.3 |
Example 30 25 4 7 0.007 1.3 0.4 O 0 0
Example 35 1 -13 0.017 3.2 more than 1.0 XXX comparative 7 Example 35 2 -21 0.019 4.1 more than 1.0 impossible to - X comparative 8 undergo false twisting Example 35 4 -23 0.023 4.3 more than 1.0 impossible to - X comparative 9 undergo false twisting
Table 7
Table 8
(Note) GD; stretching roller
t H or U1 O
Table 9 Width Diameter Weight of Difference Percentage Difference Property Qualification of winding in the of the total appearance winding winding of the dent diameter unwinding tension of dyeing of the coil J of (%) unwinds bobbin coil (kg ) coiling of AF (nm) (nm) (mm) (cN / dtex) Example 50 300 2.4 13 18 0.010 XXX comparative 13
Example 42 85 300 4.4 6 8 0.004 ·
Example 43 110 300 5.8 4 7 0.005
Example 44 190 300 10.2 4 6 0.006 V
Example 300 200 6.8 3 5 0.010 X X Comparative X 14
? or
Table 10
Speed of 500 800 100 1300 unwound u (m / min)
Fiber coil 0.001 0.002 0.004 0.006 conjugate in Example 32 (cN / dtex)
Fiber coil 0.006 0.009 0.011 0.014 conjugate in Comparative Example 14 (cN / dtex)
Table 11
ABILITY TO USE IN THE INDUSTRY
The polyester-type conjugate fiber coil according to the present invention is capable of being supplied to knitting / weaving processes as such or after having been subjected to a false and stretched twist texturing process. The resulting fabric is free of irregularities of periodic dyeing, it is excellent in terms of appearance quality and shape recovery properties after stretching. Furthermore, by using the polyester-type conjugate fiber coil according to the present invention, it is possible to obtain a good quality twisted texturized yarn. Particularly, the present invention is useful to provide a conjugate fiber coil of polyester type suitable for industrial production.
Claims (23)
1. A polyester type conjugate fiber coil of side-by-side type or cover type / eccentric core in which two kinds of polyester components adhere together to form a single filament, wherein at least one of the components consists of of a single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more, which coil is formed of two kg or more of the conjugated fiber and satisfies the following conditions (1) to (3) ): (1) the difference in diameter between the edge portion and the central portion of the coil is 10 mm or less, (2) the winding width of the coil is in a range of 60 to 250 mm and the diameter of the coil is in a range of 100 to 400 mm, and (3) the difference in the value of dry heat shrinkage stress between the conjugate fibers stratified in the edge portion and the central portion of the coil is 0.05 cN / dtex or less.
2. The polyester-type conjugate fiber coil as described in claim 1, wherein the difference in the dry heat shrink tension value between the laminated conjugate fibers in the edge portion and the central portion of the coil is 0.01 cN / dtex or less.
3. The polyester-type conjugate fiber coil as described in claim 1 or 2, wherein the conjugate fiber stratified in the coil is a preoriented conjugate fiber having an elongation to rupture in a range of 60 to 120% .
4. The polyester-type conjugate fiber coil as described in claim 1 or 2, wherein the conjugate fiber stratified in the coil is a stretched conjugate fiber having an elongation to rupture in a range of 25 to 80% .
5. The polyester type conjugate fiber coil as described in any of claims 1 to 4, wherein the U% value of yarn fineness variation of the unwound conjugate fiber of the coil is 1.5% or less and the coefficient of variation of the yarn fineness variation period is 0.4 or less.
6. The polyester type conjugate fiber coil as described in any of claims 1 to 5, wherein the ratio between the difference ñF (cN / dtex) in the unwinding tension during unwinding of the conjugate fiber from the coil and the uncoiling speed u (m / min) satisfies the following formula (1): AF = 8.0 X 106 u - (1)
7. The polyester-type conjugate fiber coil as described in any of claims 1 to 6, wherein the percentage of coil dents is 12% or less. The polyester-type conjugate fiber coil as described in any of claims 1 to 7, wherein the stretch elongation Ve of the stratified conjugate fiber in the edge portion of the coil is 20% or less before to be treated with boiling water. 9. The polyester type conjugate fiber coil as described in any of claims 1 to 8, wherein the hardness of the edge portion of the coil is in a range of 50 to 90 and the difference in hardness between opposite shore portions is 10 or less. 10. The polyester type conjugate fiber coil as described in any of claims 1 to 9, wherein the coil density is in a range of 0.80 to 0.92 g / cm3. 11. The polyester-type conjugate fiber coil as described in any of claims 1 to 10, wherein any of the two classes of polyester components is polytrimethylene terephthalate containing 90 mol% or more of the repeating units. of trimethylene terephthalate. 12. A pre-oriented conjugate fiber of polyester type either side-by-side type or sheath / eccentric core type in which two kinds of polyester components adhere to form a single filament, wherein at least one of the components consists of a single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mole percent or more and wherein the preoriented conjugated fiber is coiled to form a coil and satisfies the following conditions (1) to (4): (1) a stretched elongation before being treated with boiling water is less than 20%, (2) an elongation at break is in a range of 60 to 120% , (3) a dry heat shrink tension value is in a range of 0.01 to 0.15 cN / dtex and (4) a U% value of yarn fineness variation is 1.5% or less and the coefficient of variation of the Thread fineness variation period is 0.4 or less. 13. The stretched conjugated fiber of polyester type either side-by-side type or eccentric sheath / core type in. which two kinds of polyester components adhere to each other to form a single filament, wherein at least one of the components consists of a single filament which is polytrimethylene terephthalate containing repeating units of trimethylene terephthalate of 90 mol% or further, and wherein the conjugate and drawn fiber is wound to form a coil and satisfies the following conditions (5) to (8): (5) a stretch elongation CE2 measured after the conjugate fiber has been treated with water in boiling under a load of 2 x 10"3 cN / dtex that is in a range of 5 to 100%, (6) an elongation at break that is in a range of 25 to 80%, (7) a voltage value of shrinkage by dry heat that is in a range of 0.02 to 0.24 cN / dtex, and (8) a value U% of variation of fineness of yarn that is 1.5% or less and a coefficient of variation of a period of variation of fineness of thread of 0.4 or less 14. Conjugated fiber of p type oliester as described in claim 12 or 13, wherein the fiber-fiber dynamic friction coefficient of the conjugate fiber is in a range of 0.20 to 0.35 and the difference between the maximum and minimum values of the dynamic friction coefficient in the direction of Thread length is 0.05 or less. 15. The conjugate fiber of polyester type as described in any of claims 12 to 14, wherein the difference in the yarn length direction between the maximum and minimum values of a tension value at 10% elongation in the Measurement of tensions and elongations is 0.30 cN / dtex or less. 16. The conjugate fiber of polyester type as described in any of claims 12 to 15, wherein a modified cross-sectional degree of the conjugate fiber is in a range of 1 to 5. 17. Textile twisted yarn in false of conjugated fiber of the polyester type obtained by the false twist texturing of the conjugated fiber of the polyester type by any of claims 1 to 16, which satisfies the following conditions (a) and (b): (a) a resistance tensile which is in a range of 2 to 4 cN / dtex and (b) a stretch elongation CE2 measured after it is treated with boiling water under a load of 2 x 10 ~ 3 cN / dtex which is in a 50 to 250% range. 1
8. A method for producing a polyester-type conjugate fiber coil of either the side-to-side type or the eccentric sheath / core type in which the two kinds of polyester components adhere to each other to form a single filament; at least one of the components consists of. a single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more; and the conjugate fiber is spun by a melt spinning method and is wound on the coil while it is cooled and solidified by cooling air, where the spinning process is carried out by maintaining a spinning tension at 0.3 cN / dtex or less, a coil temperature of 30 ° C or less and a winding speed in a range of 1500 to 4000 m / min. 1
9. A method for producing a pre-oriented conjugate fiber coil of the polyester type either side-by-side or sheath / eccentric core type in which two kinds of polyester components adhere to form a single filament; at least one of the components consists of a single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more; and the conjugate fiber is spun by the melt spinning method and is wound into a coil without stretching the conjugate fiber after it is cooled and solidified by cooling air, where the winding is carried out under conditions that satisfy the Subsequent subsections (a) to (e): (a) A spinneret is used to secure the spinning condition after the two kinds of polyester components remain together, which have a dimensional ratio L / D of 2 or more where L is the length of the hole? D is an orifice diameter and the orifice is inclined at an angle of 10 to 40 degrees relative to the vertical direction, (b) the spinning tension is in a range of 0.10 to 0.30 cN / dtex, (c) the temperature Heat treatment is in a range of 70 to 120 ° C and the heat treatment tension is in a range of 0.02 to 0.10 cN / dtex, (d) the coil temperature is 30 ° C or less when the fiber conjugate is wound in a coiler, and (e) the winding speed is in a range of 1500 to 4000 m / min. 20. A method for producing a polyester-type drawn conjugate fiber coil of either the side-to-side type or the eccentric sheath / core type in which two kinds of polyester components adhere to form a single filament; at least one of the components consists of the single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more; and the conjugate fiber is spun by a melt spinning method and is wound on a coil as stretched conjugate fiber which is obtained by directly stretching the conjugate fiber without being wound once, in the coil after it is cooled and solidified by air of refining, where the winding is carried out under the condition satisfying the following items (a) and (f) to (h): (a) a row is used to ensure the condition of spinning after both Classes of polyester components are joined, which has a dimensional ratio L / D of 2 or more where L is an orifice length and D is an orifice diameter and the orifice is inclined at an angle of 10 to 40 degrees in relation to the vertical direction, (f) the drawing tension is in a range of 0.05 to 0.40 cN / dtex, (g) the VR velocity of the second heated drawn roll is in a range of 200 to 4000 m / min, (h) ) the VW / VR ratio of a winding speed Vw (m / m) in) with respect to the speed VR (m / min) of the heated second drawing roller satisfies the following formula (2): 0.85 = VW / VR = 1 --- (2) and (i) the temperature of the coil, when the The conjugate fiber is wound on the winder, is 30 ° C or less. 21. A method for producing a polyester-type conjugate fiber coil as described in claim 20, wherein the heat treatment under tension is carried out between a heated second drawing roll and a heated third drawing roll. 22. A method for producing a polyester-type conjugate fiber spool as described in any of claims 18 to 21, wherein the transverse angle of the coil is changed from the start to the end of the formation of the coil in a range of 3 to 10 degrees in correspondence with the winding diameter of the coil. 23. A method for false twist texturing of preoriented conjugate fiber of the polyester type either side-by-side type or eccentric sheath / core type in which two kinds of polyester components adhere to form a filament only; at least one of the components consists of the single filament which is polytrimethylene terephthalate containing repeated units of trimethylene terephthalate of 90 mol% or more and the conjugate fiber is spun by a melt spinning method and is wound on the coil and The pre-oriented conjugate fiber is unstretched after it is cooled and solidified by cooling air, where the spinning tension is controlled at 0.30 cN / dtex or less and the spool temperature is maintained at 30 ° during the winding. C or less and the texturing by false and stretched twisting, or the texturing by false twisting is carried out by maintaining the temperature of the conjugate fiber preorientated by 30 ° C not only during the winding procedure. but also during the storage period as well as the false twist texturing procedure thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP2001340286 | 2001-11-06 | ||
JP2001393491 | 2001-12-26 | ||
PCT/JP2002/011382 WO2003040011A1 (en) | 2001-11-06 | 2002-10-31 | Polyester composite fiber package |
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MXPA04004233A true MXPA04004233A (en) | 2004-11-29 |
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Family Applications (1)
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MXPA04004233A MXPA04004233A (en) | 2001-11-06 | 2002-10-31 | Polyester composite fiber package. |
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US (2) | US6824869B2 (en) |
EP (1) | EP1443009B1 (en) |
JP (1) | JP4079884B2 (en) |
KR (1) | KR100590129B1 (en) |
CN (1) | CN1283540C (en) |
AT (1) | ATE417016T1 (en) |
DE (1) | DE60230311D1 (en) |
ES (1) | ES2315410T3 (en) |
MX (1) | MXPA04004233A (en) |
TW (1) | TWI240022B (en) |
WO (1) | WO2003040011A1 (en) |
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2002
- 2002-10-31 ES ES02775460T patent/ES2315410T3/en not_active Expired - Lifetime
- 2002-10-31 DE DE60230311T patent/DE60230311D1/en not_active Expired - Lifetime
- 2002-10-31 JP JP2003542066A patent/JP4079884B2/en not_active Expired - Fee Related
- 2002-10-31 EP EP02775460A patent/EP1443009B1/en not_active Expired - Lifetime
- 2002-10-31 MX MXPA04004233A patent/MXPA04004233A/en not_active Application Discontinuation
- 2002-10-31 CN CNB028222075A patent/CN1283540C/en not_active Expired - Fee Related
- 2002-10-31 WO PCT/JP2002/011382 patent/WO2003040011A1/en active Application Filing
- 2002-10-31 AT AT02775460T patent/ATE417016T1/en not_active IP Right Cessation
- 2002-10-31 KR KR1020047006746A patent/KR100590129B1/en not_active IP Right Cessation
- 2002-11-04 US US10/286,894 patent/US6824869B2/en not_active Expired - Fee Related
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EP1443009A4 (en) | 2006-03-08 |
EP1443009A1 (en) | 2004-08-04 |
KR100590129B1 (en) | 2006-06-19 |
ES2315410T3 (en) | 2009-04-01 |
CN1582250A (en) | 2005-02-16 |
DE60230311D1 (en) | 2009-01-22 |
CN1283540C (en) | 2006-11-08 |
JP4079884B2 (en) | 2008-04-23 |
ATE417016T1 (en) | 2008-12-15 |
WO2003040011A1 (en) | 2003-05-15 |
US6824869B2 (en) | 2004-11-30 |
EP1443009B1 (en) | 2008-12-10 |
US20030143395A1 (en) | 2003-07-31 |
TW200303379A (en) | 2003-09-01 |
JPWO2003040011A1 (en) | 2005-02-24 |
US20050084676A1 (en) | 2005-04-21 |
KR20040068131A (en) | 2004-07-30 |
TWI240022B (en) | 2005-09-21 |
US6982118B2 (en) | 2006-01-03 |
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